Metallocene compositions

ABSTRACT

This invention relates to metallocene compositions and their use in the preparation of catalyst systems for olefin polymerization, particularly propylene polymerization. The metallocene compositions may be represented by the formula:                    
     wherein R 9  and R 11  are identical or different and are a Group 14 radical having from 1 to 20 carbon atoms or are each primary, secondary or tertiary butyl groups, aryl groups, isopropyl groups, fluoroalkyl groups, trialkyl silyl groups, or other groups of similar size.

This application is a divisional of U.S. patent application Ser. No.09/620,304, filed Jul. 19, 2000, now U.S. Pat. No. 6,376,412, which isbased on U.S. Provisional Patent Application Ser. No. 60/215,459, filedJun. 30, 2000.

FIELD

This invention relates to metallocene compositions and their use in thepreparation of catalyst systems for olefin polymerization, particularlypropylene polymerization.

BACKGROUND

The use of metallocene compositions in olefin polymerization is wellknown. Metallocenes containing substituted, bridged indenyl derivativesare noted for their ability to produce isotactic propylene polymershaving high isotacticity and narrow molecular weight distribution.Considerable effort has been made toward obtaining metallocene producedpropylene polymers having ever-higher molecular weight and meltingpoint, while maintaining suitable catalyst activity.

Toward this end researchers have found that there is a directrelationship between the way in which a metallocene is substituted, andthe molecular structure of the resulting polymer. For the substituted,bridged indenyl type metallocenes, it is now well established that thetype and arrangement of substituents on the indenyl groups, as well asthe type of bridge connecting the indenyl groups, determines suchpolymer attributes as molecular weight and melting point. Unfortunately,it is impossible at this time to accurately correlate specificsubstitution patterns with specific polymer attributes, though trendsmay be identified.

For example, U.S. Pat. No. 5,840,644 describes certain metallocenescontaining aryl-substituted indenyl derivatives as ligands, which aresaid to provide propylene polymers having high isotacticity, narrowmolecular weight distribution and very high molecular weight.

Likewise, U.S. Pat. No. 5,936,053 describes certain metallocenecompounds said to be useful for producing high molecular weightpropylene polymers. These metallocenes have a specific hydrocarbonsubstituent at the 2 position and an unsubstituted aryl substituent atthe 4 position, on each indenyl group of the metallocene compound.

WO 98/40419 and WO 99/42497 both describe certain supported catalystsystems for producing propylene polymers having high melting point.Metallocene compositions and their activators are often combined with asupport material in order to obtain a catalyst system that is lesslikely to cause reactor fouling. However, it is known that supportedmetallocene catalyst systems tend to result in a polymer having lowermelting point than would otherwise be obtained if the metallocene werenot supported.

Much of the current research in this area has been directed toward usingmetallocene catalyst systems under commercially relevant processconditions, to obtain propylene polymers having melting points higherthan known metallocene catalyst systems and close to, or as high as,propylene polymers obtained using conventional, Ziegler-Natta catalystsystems, i.e., 160° C. or higher. The present inventors have discoveredmetallocene compounds that not only have this capability, but retain itupon supportation.

SUMMARY

The present invention relates to novel metallocene compositions capableof providing propylene polymers having high melting point and molecularweight. The present invention further relates to metallocene catalystsystems comprising one or more of these compositions and one or moreactivators or cocatalysts, and optionally, support material, and to theuse of such metallocene catalyst systems in olefin polymerization,particularly propylene polymer polymerization.

DESCRIPTION

The metallocenes of the present invention are represented by theformula:

wherein: M¹ is selected from the group consisting of titanium,zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenumand tungsten, preferably zirconium, hafnium or titanium, most preferablyzirconium;

R¹ and R² are identical or different, and are one of a hydrogen atom, aC₁-C₁₀ alkyl group, a C₁-C₁₀ alkoxy group, a C₆-C₁₀ aryl group, a C₆-C₁₀aryloxy group, a C₂-C₁₀ alkenyl group, a C₂-C₄₀ alkenyl group, a C₇-C₄₀arylalkyl group, a C₇-C₄₀ alkylaryl group, a C₈-C₄₀ arylalkenyl group,an OH group or a halogen atom; R¹ and R² may also be joined together toform an alkanediyl group or a conjugated C₄₋₄₀ diene ligand which iscoordinated to M¹ in a metallocyclopentene fashion; R¹ and R² may alsobe identical or different conjugated dienes, optionally substituted withone or more hydrocarbyl, tri(hydrocarbyl)silyl groups or hydrocarbyl,tri(hydrocarbyl)silylhydrocarbyl groups, said dienes having up to 30atoms not counting hydrogen and forming a π complex with M, examplesinclude 1,4-diphenyl-1,3-butadiene, 1,3-pentadiene,2-methyl-1,3-pentadiene, 2,4-hexadiene, 1-phenyl-1,3-pentadiene,1,4-dibenzyl-1,3-butadiene, 1,4-ditolyl-1,3-butadiene,1,4-bis(trimethylsilyl)-1,3-butadiene, and 1,4-dinaphthyl-1,3-butadiene;

preferably R¹ and R² are identical and are a C₁-C₃ alkyl or alkoxygroup, a C₆-C₈ aryl or aryloxy group, a C₂-C₄ alkenyl group, a C₇-C₁₀arylalkyl group, a C₇-C₁₂ alkylaryl group, or a halogen atom, preferablychlorine;

R³ are identical or different and are each a hydrogen atom, a halogenatom, a C₁-C₁₀ alkyl group which may be halogenated, a C₆-C₁₀ aryl groupwhich may be halogenated, a C₂-C₁₀ alkenyl group, a C₇-C₄₀-arylalkylgroup, a C₇-C₄₀ alkylaryl group, a C₈-C₄₀ arylalkenyl group, a —NR′₂,—SR′, —OR′, —OSiR′₃ or —PR′₂ radical, wherein R′ is one of a halogenatom, a C₁-C₁₀ alkyl group, or a C₆-C₁₀ aryl group; preferably R³ is nota hydrogen atom;

preferably each R³ is identical and is a fluorine, chlorine or bromine,atom, a C₁-C₄ alkyl group which may be halogenated, a C₆-Cg aryl groupwhich may be halogenated, a —NR′₂, —SR′, —OR, —OSiR′₃ or —PR′₂ radical,wherein R′ is one of a chlorine atom, a C₁-C₄ alkyl group, or a C₆-C₈aryl group;

more preferably, R³ are identical and are each a C₃ alkyl group, mostpreferably isopropyl groups;

alternatively, R³ is a C₁ or C₂ alkyl group;

R⁴ to R⁷ are identical or different and are hydrogen, or are as definedfor R³ or two or more adjacent radicals R⁵ to R⁷ together with the atomsconnecting them form one or more rings, preferably a 6-membered ring,preferably 4-8 membered ring;

—B(R¹⁴)—, —Al(R¹⁴)—, —Ge—, —Sn—, —O—, —S—, —SO—, —SO₂—, —N(R¹⁴)—, —CO—,—P(R¹⁴)—, or —P(O)(R¹⁴)—;

wherein: R¹⁴, R¹⁵ and R¹⁶ are identical or different and are a hydrogenatom, a halogen atom, a C₁-C₂₀ branched or linear alkyl group, a C₁-C₂₀to fluoroalkyl or silaalkyl group, a C₆-C₃₀ aryl group, a C₆-C₃₀fluoroaryl group, a C₁-C₂₀ alkoxy group, a C₂-C₂₀ alkenyl group, aC₇-C₄₀ arylalkyl group, a C₈-C₄₀ arylalkenyl group, a C₇-C₄₀ alkylarylgroup, or R¹⁴ and R¹⁵, together with the atoms binding them, form acyclic ring;

preferably, R¹⁴, R¹⁵ and R¹⁶ are identical and are a hydrogen atom, ahalogen atom, a C₁-C₄ alkyl group, a CF₃ group, a C₆-C₈ aryl group, aC₆-C₁₀ fluoroaryl group, more preferably a pentafluorophenyl group, aC₁-C₄ alkoxy group, in particular a methoxy group, a C₂-C₄ alkenylgroup, a C₇-C₁₀ arylalkyl group, a C₈-C₁₂ arylalkenyl group, or a C₇-C₁₄alkylaryl group;

or, R¹³ is represented by the formula:

wherein: R¹⁷ to R²⁴ are as defined for R¹ and R², or two or moreadjacent radicals R¹⁷ to R²⁴, including R²⁰ and R²¹, together with theatoms connecting them form one or more rings, preferably, R¹⁷ to R²⁴ arehydrogen;

M² is one or more carbons, silicon, germanium or tin, preferablysilicon;

R¹³ may also be an amidoborane-type radical such as is described inWO0/20426 (herein fully incorporated by reference);

R⁸, R¹⁰ and R¹² are identical or different and have the meanings statedfor R⁴ to R⁷; and

R⁹ and R¹¹ are identical or different and are a Group IVA radical havingfrom 1 to 20 carbon atoms or are each primary, secondary or tertiarybutyl groups, aryl groups, isopropyl groups, fluoroalkyl groups,trialkyl silyl groups, or other groups of similar size, preferably atertiary butyl group.

In another embodiment, the metallocenes of the present invention arerepresented by the formula:

wherein: M¹ is selected from the group consisting of titanium zirconium,hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten;

R¹ and R² are identical or different, and are one of a hydrogen atom, aC₁-C₁₀ alkyl group, a C₁-C₁₀ alkoxy group, a C₆-C₁₀ aryl group, a C₆-C₁₀aryloxy group, a C₂-C₁₀ alkenyl group, a C₂-C₄₀ alkenyl group, a C₇-C₄₀arylalkyl group, a C₇-C₄₀ alkylaryl group, a C₉-C₄₀ arylalkenyl group,an OH group or a halogen atom, or a conjugated diene which is optionallysubstituted with one or more hydrocarbyl, tri(hydrocarbyl)silyl groupsor hydrocarbyl, tri(hydrocarbyl)silylhydrocarbyl groups, said dienehaving up to 30 atoms not counting hydrogen;

R³ are identical or different and are each a halogen atom, a C₃-C₁₀alkyl group which may be halogenated, a C₆-C₁₀ aryl group which may behalogenated, a C₂-C₁₀ alkenyl group, a C₇-C₄₀-arylalkyl group, a C₇-C₄₀alkylaryl group, a C₉-C₄₀ arylalkenyl group, a —NR′₂, —SR′, —OR′,—OSiR′₃ or —PR′₂ radical, wherein R is one of a halogen atom, a C₁-C₁₀alkyl group, or a C₆-C₁₀ aryl group;

R⁴ to R⁷ are identical or different and are hydrogen, as defined for R³or two or more adjacent radicals R⁵ to R⁷ together with the atomsconnecting them form one or more rings;

—B(R¹⁴)—, —Al(R¹⁴)—, —Ge—, —Sn—, —O—, —S—, —SO—, —SO₂—, —N(R¹⁴)—, —CO—,—P(R¹⁴) or —P(O)(R¹⁴)—, or an amidoborane radical;

wherein: R¹⁴, R¹⁵ and R¹⁶ are identical or different and are a hydrogenatom, a halogen atom, a C₁-C₂₀ alkyl group, a C₁-C₂₀ fluoroalkyl orsilaalkyl group, a C₆-C₃₀ aryl group, a C₆-C₃₀ fluoroaryl group, aC₁-C₂₀ alkoxy group, a C₂-C₂₀ alkenyl group, a C₇-C₄₀ arylalkyl group, aC₈-C₄₀ arylalkenyl group, a C₇-C₄₀ alkylaryl group, or R¹⁴ and R¹⁵,together with the atoms binding them, form a cyclic ring;

or, R¹³ is represented by the formula:

wherein: R¹⁷ to R²⁴ are as defined for R¹ and R², or two or moreadjacent radicals R¹⁷ to R²⁴, including R²⁰ and R²¹, together with theatoms connecting them form one or more rings;

M² is one or more carbons, silicon, germanium or tin;

R⁸, R¹⁰ and R¹² are identical or different and have the meanings statedfor R⁴ to R⁷; and

R⁹ and R¹¹ are identical or different and are each a Group IVA radicalhaving from 2 to 20 carbon atoms or are each a primary, secondary ortertiary butyl group, an aryl group, an isopropyl group, trialkyl silylgroup, or a is fluoroalkyl group.

In another embodiment the metallocenes of this invention are representedby the formula:

wherein: M¹ is selected from the group consisting of titanium,zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenumand tungsten;

R¹ and R² are identical or different, and are one of a hydrogen atom, aC₁-C₁₀ alkyl group, a C₁-C₁₀ alkoxy group, a C₆-C₁₀ aryl group, a C₆-C₁₀aryloxy group, a C₂-C₁₀ alkenyl group, a C₂-C₄₀ alkenyl group, a C₇-C₄₀arylalkyl group, a C₇-C₄₀ alkylaryl group, a C₈-C₄₀ arylalkenyl group,an OH group or a halogen atom or a conjugated diene which is optionallysubstituted with one or more hydrocarbyl, tri(hydrocarbyl)silyl groupsor hydrocarbyl, tri(hydrocarbyl)silylhydrocarbyl groups, said dienehaving up to 30 atoms not counting hydrogen;

R³ are identical or different and are each a hydrogen atom, a halogenatom, a C₁-C₁₀ alkyl group which may be halogenated, a C₆-C₁₀ aryl groupwhich may be halogenated, a C₂-C₁₀ alkenyl group, a C₇-C₄₀-arylalkylgroup, a C₇-C₄₀ alkylaryl group, a C₈-C₄₀ arylalkenyl group, a —NR′₂,—SR′, —OR′, —OSiR′₃ or —PR′₂ radical, wherein: R′ is one of a halogenatom, a C₁-C₁₀ alkyl group, or a C₆-C₁₀ aryl group;

R⁴ to R⁷ are identical or different and are hydrogen, as defined for R³or two or more adjacent radicals R⁵ to R⁷ together with the atomsconnecting them form one or more rings;

—B(R¹⁴)—, —Al(R¹⁴)—, —Ge—, —Sn—, —O—, —S—, —SO—, —SO₂—, —N(R¹⁴)—, —CO—,—P(R¹⁴)—, or —P(O)(R¹⁴), or an amidoborane radical;

wherein: R¹⁴, R¹⁵ and R¹⁶ are identical or different and are a hydrogenatom, a halogen atom, a C₁-C₂₀ alkyl group, a C₁-C₂₀ fluoroalkyl orsilaalkyl group, a C₆-C₃₀ aryl group, a C₆-C₃₀ fluoroaryl group, aC₁-C₂₀ alkoxy group, a C₂-C₂₀ alkenyl group, a C₇-C₄₀ arylalkyl group, aC₉-C₄₀ arylalkenyl group, a C₇-C₄₀ alkylaryl group, or R¹⁴ and R¹⁵,together with the atoms binding them, form a cyclic ring;

or, R¹³ is represented by the formula:

wherein: R¹⁷ to R²⁴ are as defined for R¹ and R², or two or moreadjacent radicals R¹⁷ to R²⁴, including R²⁰ and R²¹, together with theatoms connecting them form one or more rings;

M² is one or more carbons, silicon, germanium or tin;

R⁸, R¹⁰ and R¹² are identical or different and have the meanings statedfor R⁴ to R⁷; and

R⁹ and R¹¹ are identical or different and are each primary, secondary ortertiary butyl groups.

In another embodiment the metallocenes of this invention are representedby the formula:

wherein: M¹ is selected from the group consisting of titanium, zirconiumhafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten;

R¹ and R² are identical or different, and are one of a hydrogen atom, aC₁-C₁₀ alkyl group, a C₁-C₁₀ alkoxy group, a C₆-C₁₀ aryl group, a C₆-C₁₀aryloxy group, a C₂-C₁₀ alkenyl group, a C₂-C₄₀ alkenyl group, a C₇-C₄₀arylalkyl group, a C₇-C₄₀ alkylaryl group, a C₉-C₄₀ arylalkenyl group,an OH group or a halogen atom, or a conjugated diene which is optionallysubstituted with one or more hydrocarbyl, tri(hydrocarbyl)silyl groupsor hydrocarbyl, tri(hydrocarbyl)silylhydrocarbyl groups, said dienehaving up to 30 atoms not counting hydrogen;

R³ are identical and are each a C₁ or C₂ alkyl group, a C₃ alkyl groupor a C₄-C₁₀ alkyl group;

R⁴ to R⁷ are identical or different and are hydrogen, as defined for R³or two or more adjacent radicals R⁵ to R⁷ together with the atomsconnecting them form one or more rings;

—B(R¹⁴)—, —Al(R¹⁴)—, —Ge—, —Sn—, —O—, —S—, —SO—, —SO₂—, —N(R¹⁴)—, —CO—,—P(R¹⁴), or —P(O)(R¹⁴), or an amidoborane radical;

wherein: R¹⁴, R¹⁵ and R¹⁶ are identical or different and are a hydrogenatom, a halogen atom, a C₁-C₂₀ alkyl group, a C₁-C₂₀ fluoroalkyl orsilaalkyl group, a C₆-C₃₀ aryl group, a C₆-C₃₀ fluoroaryl group, aC₁-C₂₀ alkoxy group, a C₂-C₂₀ alkenyl group, a C₇-C₄₀ arylalkyl group, aC₈-C₄₀ arylalkenyl group, a C₇-C₄₀ alkylaryl group, or R¹⁴ and R¹⁵,together with the atoms binding them, form a cyclic ring;

or, R¹³ is represented by the formula:

wherein: R¹⁷ to R²⁴ are as defined for R¹ and R², or two or moreadjacent radicals R¹⁷ to R²⁴, including R²⁰ and R²¹, together with theatoms connecting them form one or more rings;

M² is one or more carbons, silicon, germanium or tin;

R⁸, R¹⁰ and R¹² are identical or different and have the meanings statedfor R⁴ to R⁷; and

R⁹ and R¹¹ are identical or different and are each primary, secondary ortertiary butyl groups.

In another embodiment the metallocenes of this invention are representedby the formula:

wherein: M¹ is selected from the group consisting of titanium,zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenumand tungsten;

R¹ and R² are identical or different, and are one of a hydrogen atom, aC₁-C₁₀ alkyl group, a C₁-C₁₀ alkoxy group, a C₆-C₁₀ aryl group, a C₆-C₁₀aryloxy to group, a C₂-C₁₀ alkenyl group, a C₂-C₄₀ alkenyl group, aC₇-C₄₀ arylalkyl group, a C₇-C₄₀ alkylaryl group, a C₈-C₄₀ arylalkenylgroup, an OH group or a halogen atom, or a conjugated diene which isoptionally substituted with one or more hydrocarbyl,tri(hydrocarbyl)silyl groups or hydrocarbyl,tri(hydrocarbyl)silylhydrocarbyl groups, said diene having up to 30atoms not counting hydrogen;

R³ are identical or different and are each a hydrogen atom, a halogenatom, a C₁-C₁₀ alkyl group which may be halogenated, a C₆-C₁₀ aryl groupwhich may be halogenated, a C₂-C₁₀ alkenyl group, a C₇-C₄₀-arylalkylgroup, a C₇-C₄₋₀ alkylaryl group, a C₈-C₄₀ arylalkenyl group, a —NR₂ ¹⁵,—SR¹⁵, —OR¹⁵, —OSiR₃ ¹⁵ or —PR₂ ¹⁵ radical, wherein: R¹⁵ is one of ahalogen atom, a C₁-C₁₀ alkyl group, or a C₆-C₁₀ aryl group;

R⁴ to R⁷ are identical or different and are hydrogen, as defined for R³or two or more adjacent radicals R⁵ to R⁷ together with the atomsconnecting them form one or more rings;

R¹³ is represented by the formula:

wherein: R¹⁷ to R²⁴ are as defined for R¹ and R², or two or moreadjacent radicals R¹⁷ to R²⁴, including R²⁰ and R²¹, together with theatoms connecting them form one or more rings;

M² is one or more carbons, silicon, germanium or tin;

R⁸, R¹⁰ and R¹² are identical or different and have the meanings statedfor R⁴ to R⁷; and

R⁹ and R¹¹ are identical or different and are each a Group IVA radicalhaving from 1 to 20 carbon atoms, a primary, secondary or tertiary butylgroup, an aryl group, an isopropyl group, trialkyl silyl group, or afluoroalkyl group.

In another embodiment the metallocenes of this invention are representedby the formula:

wherein: M¹ is selected from the group consisting of titanium zirconium)hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten;

R¹ and R² are identical or different, and are one of a hydrogen atom, aC₁-C₁₀ alkyl group, a C₁-C₁₀ alkoxy group, a C₆-C₁₀ aryl group, a C₆-C₁₀aryloxy group, a C₂-C₁₀ alkenyl group, a C₂-C₄₀ alkenyl group, a C₇-C₄₀arylalkyl group, a C₇-C₄₀ alkylaryl group, a C₈-C₄₀ arylalkenyl group,an OH group or a halogen atom, or a conjugated diene which is optionallysubstituted with one or more hydrocarbyl, tri(hydrocarbyl)silyl groupsor hydrocarbyl, tri(hydrocarbyl)silylhydrocarbyl groups, said dienehaving up to 30 atoms not counting hydrogen;

R³ are identical and are each a C₁-C₄ alkyl group;

R⁴ to R⁷ are identical or different and are hydrogen, as defined for R³or two or more adjacent radicals R⁵ to R⁷ together with the atomsconnecting them form one or more rings;

R¹³ is represented by the formula:

wherein: R¹⁷ to R²⁴ are as defined for R¹ and R², or two or moreadjacent radicals R¹⁷ to R²⁴, including R²⁰ and R²¹, together with theatoms connecting them form one or more rings;

M² is carbon, silicon, germanium or tin;

R⁸, R¹⁰ and R¹² are identical or different and have the meanings statedfor R⁴ to R⁷; and

R⁹ and R¹¹ are identical or different and are each primary, secondary ortertiary butyl groups.

As utilized herein, the term “alkyl”, alone or in combination, means astraight-chain or branched-chain alkyl radical. Examples of suchradicals include, but are not limited to, methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl,hexyl, octyl and the like. The term “alkenyl” means a straight-chain orbranched-chain hydrocarbon radial having one or more double bonds.Examples of suitable alkenyl radicals include, but are not limited to,ethenyl, propenyl, allyl, 1,4-butadienyl and the like. The term “alkoxy”means an alkyl ether radical wherein the term alkyl is as defined above.Examples of suitable alkyl ether radicals include, but are not limitedto, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, iso-butoxy,sec-butoxy, tert-butoxy and the like. The term “aryl” means a phenyl,azulenyl, or naphthyl radical and the like which optionally contains aheteroatom and/or carries one or more substituents, for example, alkyl,alkoxy, halogen, hydroxy, amino, nitro, etc.

The following are particularly preferred metallocenes:

rac-dimethylsiladiyl(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylsiladiyl(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylsiladiyl(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylsiladiyl(2-methyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafniumdichloride;

rac-dimethylsiladiyl(2-ethyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafniumdichloride;

rac-dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium

rac-dimethylsiladiyl(2-iso-propyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;

rac-dimethylsiladiyl(2-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl) ₂hafniumdichloride;

rac-9-silafluorendiyl(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-see-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-ethyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafniumdichloride;

rac-9-silafluorendiyl(2-n-propyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-tert-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dichloride;

rac-dimethylsiladiyl(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylsiladiyl(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylsiladiyl(2-i so-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylsiladiyl(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylsiladiyl(2-methyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafniumdimethyl;

rac-dimethylsiladiyl(2-ethyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafniumdimethyl;

rac-dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl

rac-dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;

rac-dimethylsiladiyl(2-n-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;

rac-dimethylsiladiyl(2-iso-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;

rac-dimethylsiladiyl(2-sec-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;

rac-dimethylsiladiyl(2-tert-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-isopropyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-sec-butyl, 4-[3′,⁵′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-ethyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂hafnium dimethyl;

rac-dimethylsiladiyl(2-methyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylsiladiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylsiladiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylsiladiyl(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylsiladiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylsiladiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylsiladiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylsiladiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylsiladiyl(2-methyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;

rac-dimethylsiladiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl) ₂hafnium dichloride;

rac-dimethylsiladiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;

rac-dimethylsiladiyl(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;

rac-dimethylsiladiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;

rac-dimethylsiladiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;

rac-dimethylsiladiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;

rac-dimethylsiladiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-methyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylsiladiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-methyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂ hafnium dichloride;

rac-9-silafluorendiyl(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂ hafnium dichloride;

rac-9-silafluorendiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dichloride;

rac-dimethylsiladiyl(2-methyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylsiladiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylsiladiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylsiladiyl(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylsiladiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylsiladiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylsiladiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylsiladiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylsiladiyl(2-methyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;

rac-dimethylsiladiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;

rac-dimethylsiladiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;

rac-dimethylsiladiyl(2-isopropyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;

rac-dimethylsiladiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;

rac-dimethylsiladiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;

rac-dimethylsiladiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;

rac-dimethylsiladiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-methyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylsiladiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-isobutyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-methyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂ hafnium dimethyl;

rac-9-silafluorendiyl(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂ hafnium dimethyl;

rac-9-silafluorendiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂hafnium dimethyl;

rac-dimethylsiladiyl(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylsiladiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylsiladiyl(2-ethyl, 4-[3′,5′-iso-propylphenyl]indenyl)₂hafnium dichloride;

rac-dimethylsiladiyl(2-n-propyl,4-[3′,5′-iso-propylphenyl]indenyl)₂hafnium dichloride;

rac-dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;

rac-dimethylsiladiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;

rac-dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;

rac-dimethylsiladiyl(2-so-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;

rac-dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-tert-butyl,4[31,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dichloride;

rac-dimethylsiladiyl(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylsiladiyl(2-isopropyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylsiladiyl(2-n-butyl, 4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylsiladiyl(2-isobutyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylsiladiyl(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;

rac-dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;

rac-dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;

rac-dimethylsiladiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;

rac-dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylsiladiyl(2-tert-butyl,4-[31,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-ethyl, 4-[3′,5′-di-iso-propylphenyl]indenyl)2hafnium dimethyl;

rac-9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂hafnium dimethyl;

rac-dimethylsiladiyl(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylsiladiyl(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)zirconium dichloride;

rac-dimethylsiladiyl(2-n-butyl,4-[31,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylsiladiyl(2-methyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdichloride;

rac-dimethylsiladiyl(2-ethyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdichloride;

rac-dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;

rac-dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;

rac-dimethylsiladiyl(2-n butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;

rac-dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;

rac-dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;

rac-dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)zirconium dichloride;

rac-9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-9-silafluorendiyl(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-ethyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdichloride;

rac-9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-iso-butyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;

rac-9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dichloride;

rac-dimethylsiladiyl(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylsiladiyl(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylsiladiyl(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylsiladiyl(2-methyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdimethyl;

rac-dimethylsiladiyl(2-ethyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdimethyl;

rac-dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;

rac-dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;

rac-dimethylsiladiyl(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;

rac-dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;

rac-dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;

rac-dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-9-silafluorendiyl(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-ethyl, 4-[3′,5′-di-phenylphenyl]indenyl)₂hafniumdichloride;

rac-9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;

rac-9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂hafnium dimethyl;

rac-dimethylsiladiyl(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylsiladiyl(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylsiladiyl(2-isopropyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylsiladiyl(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylsiladiyl(2-sec-butyl,4-[31,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylsiladiyl(2-tert-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylsiladiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylsiladiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylsiladiyl(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylsiladiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylsiladiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylsiladiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylsiladiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylsiladiyl(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylsiladiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl 1,3-butadiene;

rac-dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylsiladiyl(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylsiladiyl(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylsiladiyl(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylsiladiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylsiladiyl(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylsiladiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylsiladiyl(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylsiladiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-n-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl)-1,3-butadiene;

rac-9-silafluorendiyl(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-9-silafluorendiyl(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylamidoborane(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylamidoborane(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylamidoborane(2-n-propyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylamidoborane(2-isopropyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylamidoborane(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylamidoborane(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylamidoborane(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylamidoborane(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylamidoborane(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylamidoborane(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylamidoborane(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylamidoborane(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylamidoborane(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylamidoborane(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylamidoborane(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylamidoborane(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylamidoborane(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylamidoborane(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylamidoborane(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylamidoborane(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylamidoborane(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylamidoborane(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylamidoborane(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylamidoborane(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylamidoborane(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylamidoborane(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylamidoborane(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylamidoborane(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylamidoborane(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylamidoborane(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-dimethylamidoborane(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylamidoborane(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylamidoborane(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylamidoborane(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylamidoborane(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylamidoborane(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylamidoborane(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylamidoborane(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylamidoborane(2-ethyl, 4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylamidoborane(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylamidoborane(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylamidoborane(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylamidoborane(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylamidoborane(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylamidoborane(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylamidoborane(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylamidoborane(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylamidoborane(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylamidoborane(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylamidoborane(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylamidoborane(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylamidoborane(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylamidoborane(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylamidoborane(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylamidoborane(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylamidoborane(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylamidoborane(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylamidoborane(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylamidoborane(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylamidoborane(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-dimethylamidoborane(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylamidoborane(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylamidoborane(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylamidoborane(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylamidoborane(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylamidoborane(2-iso-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylamidoborane(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylamidoborane(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylamidoborane(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylamidoborane(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylamidoborane(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylamidoborane(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylamidoborane(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylamidoborane(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylamidoborane(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylamidoborane(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylamidoborane(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylamidoborane(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylamidoborane(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylamidoborane(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylamidoborane(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylamidoborane(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylamidoborane(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylamidoborane(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylamidoborane(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl,

rac-dimethylamidoborane(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylamidoborane(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylamidoborane(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylamidoborane(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-dimethylamidoborane(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-diisopropylamidoborane(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-diisopropylamidoborane(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-diisopropylamidoborane(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-diisopropylamidoborane(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-diisopropylamidoborane(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-diisopropylamidoborane(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-diisopropylamidoborane(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-diisopropylamidoborane(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-diisopropylamidoborane(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-diisopropylamidoborane(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-diisopropylamidoborane(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-diisopropylamidoborane(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-diisopropylamidoborane(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-diisopropylamidoborane(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-diisopropylamidoborane(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-diisopropylamidoborane(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-diisopropylamidoborane(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride

rac-diisopropylamidoborane(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-diisopropylamidoborane(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-diisopropylamidoborane(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-diisopropylamidoborane(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-diisopropylamidoborane(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-diisopropylamidoborane(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-diisopropylamidoborane(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-diisopropylamidoborane(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-diisopropylamidoborane(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-diisopropylamidoborane(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-diisopropylamidoborane(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-diisopropylamidoborane(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-diisopropylamidoborane(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-diisopropylamidoborane(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-diisopropylamidoborane(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-diisopropylamidoborane(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-diisopropylamidoborane(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-diisopropylamidoborane(2-n-butyl, 4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-diisopropylamidoborane(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-diisopropylamidoborane(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-diisopropylamidoborane(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-diisopropylamidoborane(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-diisopropylamidoborane(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-diisopropylamidoborane(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-diisopropylamidoborane(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-diisopropylamidoborane(2-iso-butyl4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-diisopropylamidoborane(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-diisopropylamidoborane(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-diisopropylamidoborane(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-diisopropylamidoborane(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂ η⁴-1,4-diphenyl-1,3-butadiene;

rac-diisopropylamidoborane(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂ η⁴-1,4-diphenyl-1,3-butadiene;

rac-diisopropylamidoborane(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-diisopropylamidoborane(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂ η⁴-1,4-diphenyl-1,3-butadiene;

rac-diisopropylamidoborane(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂ η⁴-1,4-diphenyl-1,3-butadiene;

rac-diisopropylamidoborane(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂ η⁴-1,4-diphenyl-1,3-butadiene;

rac-diisopropylamidoborane(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-diisopropylamidoborane(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-diisopropylamidoborane(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-diisopropylamidoborane(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-diisopropylamidoborane(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-diisopropylamidoborane(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-diisopropylamidoborane(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-diisopropylamidoborane(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-diisopropylamidoborane(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-diisopropylamidoborane(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-diisopropylamidoborane(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-diisopropylamidoborane(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-diisopropylamidoborane(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-diisopropylamidoborane(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-diisopropylamidoborane(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-diisopropylamidoborane(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-diisopropylamidoborane(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-diisopropylamidoborane(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-diisopropylamidoborane(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-diisopropylamidoborane(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-diisopropylamidoborane(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-diisopropylamidoborane(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-diisopropylamidoborane(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-diisopropylamidoborane(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-diisopropylamidoborane(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl

rac-diisopropylamidoborane(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-diisopropylamidoborane(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-diisopropylamidoborane(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-diisopropylamidoborane(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-diisopropylamidoborane(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-diisopropylamidoborane(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-diisopropylamidoborane(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-diisopropylamidoborane(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-diisopropylamidoborane(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-diisopropylamidoborane(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-diisopropylamidoborane(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-diisopropylamidoborane(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-diisopropylamidoborane(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-bis(trimethylsilyl)amidoborane(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dichloride;

rac-bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dichloride;

rac-bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride

rac-bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dichloride;

rac-bis(trimethylsilyl)amidoborane(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dichloride;

rac-bis(trimethylsilyl)amidoborane(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂ η⁴-1,4-diphenyl-1,3-butadiene;

rac-bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂ η⁴-1,4-diphenyl-1,3-butadiene;

rac-bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂ η⁴-1,4-diphenyl-1,3-butadiene;

rac-bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂ η⁴-1,4-diphenyl-1,3-butadiene;

rac-bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂ η⁴-1,4-diphenyl-1,3-butadiene;

rac-bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂ η⁴-1,4-diphenyl-1,3-butadiene;

rac-bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂ η⁴-1,4-diphenyl-1,3-butadiene;

rac-bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂ η⁴-1,4-diphenyl-1,3-butadiene;

rac-bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-bis(trimethylsilyl)amidoborane(2-tert-butyl, 4-[3′,5′-di-iso-propylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-bis(trimethylsilyl)amidoborane(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂ η⁴-1,4-diphenyl-1,3-butadiene;

rac-bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂ η⁴-1,4-diphenyl-1,3-butadiene;

rac-bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂η⁴-1,4-diphenyl-1,3-butadiene;

rac-bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂ η⁴-1,4-diphenyl-1,3-butadiene;

rac-bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂ η⁴-1,4-diphenyl-1,3-butadiene;

rac-bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂ η⁴-1,4-diphenyl-1,3-butadiene;

rac-bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂ η⁴-1,4-diphenyl-1,3-butadiene;

rac-bis(trimethylsilyl)amidoborane(2-methyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-di-tbutylphenyl]indenyl)₂zirconium dimethyl;

rac-bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-bis-trifluoromethylphenyl]indenyl)₂zirconium dimethyl;

rac-bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl

rac-bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-di-iso-propylphenyl]indenyl)₂zirconium dimethyl;

rac-bis(trimethylsilyl)amidoborane(2-methyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-bis(trimethylsilyl)amidoborane(2-ethyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-bis(trimethylsilyl)amidoborane(2-n-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-bis(trimethylsilyl)amidoborane(2-iso-propyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-bis(trimethylsilyl)amidoborane(2-n-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-bis(trimethylsilyl)amidoborane(2-iso-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl;

rac-bis(trimethylsilyl)amidoborane(2-sec-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl; and

rac-bis(trimethylsilyl)amidoborane(2-tert-butyl,4-[3′,5′-di-phenylphenyl]indenyl)₂zirconium dimethyl.

“9-silafluorendiyl-” refers to the substituent:

The metallocenes of this invention are prepared according to generaltechniques known from the literature, for example U.S. Pat. Nos.5,789,634 and 5,840,644 (both entirely incorporated herein byreference).

Generally, metallocenes of this type are synthesized as shown below(R⁴=H) where (a) is an aryl-coupling reaction between a4-halosubstituted indene and an aryl Grignard reagent catalyzed byNiCl2(PPh3)₂ in ether-type solvents at room temperature to reflux.Product is usually purified by column chromatography or distillation.(b) is a deprotonation via a metal salt of an alkyl anion (e.g. n-BuLi)to form an indenide followed by reaction with an appropriate bridgingprecursor (e.g. Me₂SiCl₂). Reactions are usually done in ether-typesolvents at ambient temperatures. The final product is purified bycolumn chromatography or distillation; and (c) is double deprotonationvia an alkyl anion (e.g. n-BuLi) to form a dianion followed by reactionwith a metal halide (e.g. ZrCl₄). The reactions are usually done inether-type or aromatic solvents at ambient temperatures. The finalproducts are obtained by recrystallization of the crude solids.

The metallocenes of this invention are highly active catalyst componentsfor the polymerization of olefins. The metallocenes are preferablyemployed as chiral racemates. However, it is also possible to use thepure enantiomers in the (+) or (−) form. The pure enantiomers allow anoptically active polymer to be prepared. However, the meso form of themetallocenes should be removed, since the polymerization-active center(the metal atom) in these compounds is no longer chiral due to themirror symmetry at the central metal atom and it is therefore notpossible to produce a highly isotactic polymer. If the meso form is notremoved, atactic polymer is formed in addition to isotactic polymer. Forcertain to applications this may be entirely desirable.

Rac/meso metallocene isomer separation is facilitated when metallocenescontaining certain bridging groups are prepared. We have found this tobe true when the bridging group, R¹³, is represented by the formula:

wherein M² and R¹⁷ to R²⁴ are as defined above.

Metallocenes are generally used in combination with some form ofactivator in order to create an active catalyst system. The terms“activator” and “cocatalyst” are used interchangeably and are definedherein to mean any compound or component, or combination of compounds orcomponents, capable of enhancing the ability of one or more metallocenesto polymerize olefins. Alklyalumoxanes such as methylalumoxane (MAO) arecommonly used as metallocene activators. Generally alkylalumoxanescontain 5 to 40 of the repeating units:

R(AIRO)_(x)AIR₂ for linear species and (AIRO)_(x) for cyclic species

where R is a C₁-C₈ alkyl including mixed alkyls. Compounds in which R ismethyl are particularly preferred. Alumoxane solutions, particularlymethylalumoxane solutions, may be obtained from commercial vendors assolutions having various concentrations. There are a variety of methodsfor preparing alumoxane, non-limiting examples of which are described inU.S. Pat. Nos. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419,4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032,5,248,801, 5,235,081, 5,103,031 and EP-A-0 561 476, EP-BI-0 279 586,EP-A-0 594-218 and WO 94/10180, each filly incorporated herein byreference.

Ionizing activators may also be used to activate metallocenes. Theseactivators are neutral or ionic, or are compounds such astri(n-butyl)ammonium tetrakis(pentaflurophenyl)borate, which ionize theneutral metallocene compound. Such ionizing compounds may contain anactive proton, or some other cation associated with, but not coordinatedor only loosely coordinated to, the remaining ion of the ionizingcompound. Combinations of activators may also be used, for example,alumoxane and ionizing activator combination, see for example, WO94/07928.

Descriptions of ionic catalysts for coordination polymerizationcomprised of metallocene cations activated by non-coordinating anionsappear in the early work in EP-A-0 277 003, EP-A-0 277 004 and U.S. Pat.No. 5,198,401 and WO-A-92/00333 (each incorporated herein by reference).These teach desirable methods of preparation wherein metallocenes areprotonated by an anion precursor such that an alkyl/hydride group isabstracted from a transition metal to make it both cationic andcharge-balanced by the non-coordinating anion. Suitable ionic saltsinclude tetrakis-substituted borate or aluminum salts having fluoridedaryl-constituents such as phenyl, biphenyl and napthyl.

The term “non-coordinating anion” (NCA) means an anion which either doesnot coordinate to said cation or which is only weakly coordinated tosaid cation thereby remaining sufficiently labile to be displaced by aneutral Lewis base. “Compatible” non-coordinating anions are those whichare not degraded to neutrality when the initially formed complexdecomposes. Further, the anion will not transfer an anionic substituentor fragment to the cation so as to cause it to form a neutral fourcoordinate metallocene compound and a neutral by-product from the anion.Non-coordinating anions useful in accordance with this invention arethose which are compatible, stabilize the metallocene cation in thesense of balancing its ionic charge at +1, yet retain sufficientlability to permit displacement by an ethylenically or acetylenicallyunsaturated monomer during polymerization.

The use of ionizing ionic compounds not containing an active proton butcapable of producing both the active metallocene cation and anon-coordinating anion is also known. See, for example, EP-A-0 426 637and EP-A-0 573 403 (each incorporated herein by reference). Anadditional method of making the ionic catalysts uses ionizing anionprecursors which are initially neutral Lewis acids but form the cationand anion upon ionizing reaction with the metallocene compounds, forexample the use of tris(pentafluorophenyl) borane. See EP-A-0 520 732(incorporated herein by reference). Ionic catalysts for additionpolymerization can also be prepared by oxidation of the metal centers oftransition metal compounds by anion precursors containing metallicoxidizing groups along with the anion groups, see EP-A-0 495 375(incorporated herein by reference).

Where the metal ligands include halogen moieties (for example,bis-cyclopentadienyl zirconium dichloride) which are not capable ofionizing abstraction under standard conditions, they can be convertedvia known alkylation reactions with organometallic compounds such aslithium or aluminum hydrides or alkyls, alkylalumoxanes, Grignardreagents, etc. See EP-A-0 500 944 and EP-A1-0 570 982 (each incorporatedherein by reference) for in situ processes describing the reaction ofalkyl aluminum compounds with dihalo-substituted metallocene compoundsprior to or with the addition of activating anionic compounds.

Methods for supporting ionic catalysts comprising metallocene cationsand NCA are described in WO 9950311, U.S. Pat. Nos. 5,643,847 and5,972,823, U.S. patent application Ser. No. 09/184,358, filed Nov. 2,1998 and U.S. patent application Ser. No. 09/184,389, filed Nov. 2, 1998(each fully incorporated herein by reference).

When the activator for the metallocene supported catalyst composition isa NCA, preferably the NCA is first added to the support compositionfollowed by the addition of the metallocene catalyst. When the activatoris MAO, preferably the MAO and metallocene catalyst are dissolvedtogether in solution. The support is then contacted with theMAO/metallocene catalyst solution. Other methods and order of additionwill be apparent to those skilled in the art.

The catalyst systems used to prepare the compositions of this inventionare preferably supported using a porous particulate material, such asfor example, talc, inorganic oxides, inorganic chlorides such asmagnesium chloride, and resinous materials such as polyolefin orpolymeric compounds.

Preferably, the support materials are porous inorganic oxide materials,which include those from the Periodic Table of Elements of Groups 2, 3,4, 5, 13 or 14 metal/metalloid oxides. Silica, alumina, silica-alumina,and mixtures thereof are particularly preferable. Other inorganic oxidesthat may be employed either alone or in combination with the silica,alumina or silica-alumina are magnesia, titania, zirconia, and the like.

Preferably the support material is porous silica which has a surfacearea in the range of from 10 to 700 m²/g, a total pore volume in therange of from 0.1 to 4.0 cc/g and an average particle size in the rangeof from 10 to 500 Mm. More preferably, the surface area is in the rangeof from 50 to 500 m²/g, the pore volume is in the range of from 0.5 to3.5 cc/g and the average particle size is in the range of from 20 to 200lm. Most desirably the surface area is in the range of from 100 to 400m²/g, the pore volume is in the range of from 0.8 to 3.0 cc/g and theaverage particle size is in the range of from 30 to 100 μm. The averagepore size of typical porous support materials is in the range of from 10to 1000 Å. Preferably, a support material is used that has an averagepore diameter of from 50 to 500 Å, and most desirably from 75 to 350 Å.It may be particularly desirable to dehydrate the silica at atemperature of from 100° C. to 800° C. anywhere from 3 to 24 hours.

The metallocene, activator and support material may be combined in anynumber of ways. More than one metallocene may also be used. Examples ofsuitable support techniques are described in U.S. Pat. Nos. 4,808,561and 4,701,432 (each fully incorporated herein by reference). Preferablythe metallocenes and activator are combined and their reaction productsupported on the porous support material as described in U.S. Pat. No.5,240,894 and WO 94/28034, WO 96/00243, and WO 96/00245 (each fullyincorporated herein by reference.) Alternatively, the metallocenes maybe preactivated separately and then combined with the support materialeither separately or together. If the metallocenes are separatelysupported, then preferably, they are dried then combined as a powderbefore use in polymerization.

Regardless of whether the metallocene(s) and their activator areseparately precontacted or whether the metallocene(s) and activator arecombined at once, in some instances it may be preferred that the totalvolume of reaction solution applied to porous support is less than 4times the total pore volume of the porous support, more preferably lessthan 3 times the total pore volume of the porous support and even morepreferably in the range of from more than 1 to less than 2.5 times thetotal pore volume of the porous support. Procedures for measuring thetotal pore volume of porous support are well known in the art. One suchmethod is described in Volume 1, Experimental Methods in CatalystResearch, Academic Press, 1968, pages 67-96.

The supported catalyst system may be used directly in polymerization orthe catalyst system may be prepolymerized using methods well known inthe art. For details regarding prepolymerization, see U.S. Pat. Nos.4,923,833 and 4,921,825, and EP 0 279 863 and EP 0 354 893 (each fullyincorporated herein by reference).

The metallocene catalyst systems described herein are useful in thepolymerization of all types of olefins. This includes polymerizationprocesses which produce homopolymers, copolymers, terpolymers and thelike as well as block copolymers and impact copolymers. Thesepolymerization processes may be carried out in solution, in suspensionor in the gas phase, continuously or batchwise, or any combinationthereof, in one or more steps, preferably at a temperature of from 60°C. to 200° C., more preferably from 30° C. to 80° C., particularlypreferably from 50° C. to 80° C. The polymerization or copolymerizationis carried out using olefins of the formula R^(a)CH═CH—R^(b). In thisformula, R^(a) and R^(b) are identical or different and are a hydrogenatom or an alkyl radical having 1 to 14 carbon atoms. However, R^(a) andR^(b) may alternatively form a ring together with the carbon atomsconnecting them. Examples of such olefins are ethylene, propylene,1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, norbornene andnorbornadiene. In particular, propylene and ethylene are polymerized.The metallocenes and metallocenes catalyst systems of this invention aremost suitable for the polymerization of propylene based polymers.

If necessary, hydrogen is added as a molecular-weight regulator and/orin order to increase the activity. The overall pressure polymerizationsystem is from 0.5 to 100 bar. Polymerization is preferably carried outin the industrially particularly interesting pressure range from 5 to 64bar.

Typically, the metallocene is used in the polymerization in aconcentration, based on the transition metal, of from 10⁻³ to 10⁻⁸ mol,preferably from 10⁻⁴ to 10⁻⁷ mol, of transition metal per dm³ of solventor per dm³ of reactor volume. When alumoxane is used as the cocatalyst,it is used in a concentration of from 10⁻⁵ to 10⁻¹ mol, preferably from10⁻⁴ to 10⁻² mol, per dm³ of solvent or per dm³ of reactor volume. Theother cocatalysts mentioned are used in an approximately equimolaramount with respect to the metallocene. In principle, however, higherconcentrations are also possible.

If the polymerization is carried out as a suspension or solutionpolymerization, an inert solvent which is customary for the Zieglerlow-pressure process is typically used for example, the polymerizationis carried out in an aliphatic or cycloaliphatic hydrocarbon; examplesof which are propane, butane, hexane, heptane, isooctane, cyclohexaneand methylcyclohexane. It is also possible to use a benzene orhydrogenated diesel oil fraction. Toluene can also be used. Thepolymerization is preferably carried out in the liquid monomer. If inertsolvents are used, the monomers are metered in gas or liquid form.

Before addition of the catalyst, in particular of the supported catalystsystem, another alkylaluminum compound, such as, for example,trimethylaluminum, triethylaluminum, triisobutylaluminum,trioctylaluminum or isoprenylaluminum, may additionally be introducedinto the reactor in order to render the polymerization system inert (forexample to remove catalyst poisons present in the olefin). This compoundis added to the polymerization system in a concentration of from 100 to0.01 mmol of Al per kg of reactor contents. Preference is given totriisobutylaluminum and triethylaluminum in a concentration of from 10to 0.1 mmol of Al per kg of reactor contents. This allows the molarAl/M¹ ratio to be selected at a low level in the synthesis of asupported catalyst system.

In principle, however, the use of further substances for catalysis ofthe polymerization reaction is unnecessary, i.e. the systems accordingto the invention can be used as the only catalysts for thepolymerization of olefins.

The process according to the invention is distinguished by the fact thatthe metallocenes described can give propylene polymers of very highmolecular weight, melting point, and very high stereotacticity, withhigh catalyst activities in the industrially particularly interestingpolymerization temperature range of from 50° C. to 80° C.

The catalyst systems of this invention are capable of providingpolymers, particularly propylene homopolymers and copolymers, ofexceptionally high molecular weight and melting point even when used inprocesses under commercially relevant conditions of temperature,pressure and catalyst activity. Preferred melting points are at least ashigh as 155° C., more preferably at least 157° C., even more preferablyat least 157° C., and most preferably 160° C. or more.

The catalyst systems of this invention are also capable of providingpropylene polymers having high stereospecificity and regiospecificity.Isotactic propylene polymers prepared according to the processes of thisinvention may have a proportion of 2,1-inserted propene units of lessthan 0.5%, at a triad tacticity of greater than 98%. Preferably there isno measurable proportion of 2, 1-inserted propene units. Triad tacticityis determined using ¹³C-NMR according to J. C. Randall, Polymer SequenceDetermination: Carbon-13 NMR Method, Academic Press New York 1978.Polymers prepared using the processes of described herein find uses inall applications including fibers, injection-molded parts, films, pipesetc.

While the present invention has been described and illustrated byreference to particular embodiments, it will be appreciated by those ofordinary skill in the art, that the invention lends itself to manydifferent variations not illustrated herein. For these reasons, then,reference should be made solely to the appended claims for purposes ofdetermining the true scope of the present invention.

Although the appendant claims have single appendencies in accordancewith U.S. patent practice, each of the features in any of the appendantclaims can be combined with each of the features of other appendantclaims or the main claim.

EXAMPLES

All air sensitive experiments are carried out in nitrogen purged dryboxes. All solvents were purchased from commercial sources.4-Bromo-2-methyl indene, 4-chloro-2-methyl-indene and tris(perfluorophenyl) borane in toluene were purchased from commercialsources. Aluminum alkyls were purchased as hydrocarbon solutions fromcommercial sources. The commercial methylalumoxane (“MAO”) was purchasedfrom Albemarle as a 30 wt % solution in toluene. The metallocenesracemic dimethylsiladiyl(2-methyl-4-phenylindenyl)₂ zirconium dichlorideand racemic dimethylsiladiyl(4-[1-naphthy]-2-methylindenyl)₂ zirconiumdichloride were obtained from commercial sources.

Comparative Example 1 Racemicdimethylsiladiyl(2-methyl-4-phenylindenyl)₂zirconium dichlorideSupported Comparison Metallocene Catalyst System 1 Racemicdimethylsiladiyl(2-methyl-4-phenylindenyl)₂zirconium dichloride/MAO

In a 100 mL round bottom flask racemicdimethylsiladiyl(2-methyl-4-phenylindenyl)₂ zirconium dichloride(Comparison metallocene 1, 0.055 g) was added to a MAO solution (6.74 g,7.2 mL) and stirred twenty minutes. This was filtered through a mediumglass frit funnel and washed with toluene (14 mL). To the combinedfiltrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600°C. dehydration). This slurry was stirred for twenty minutes then driedat 40° C. for two minutes under vacuum on a rotary evaporator until theliquid evaporated, and then the solid was further dried a total of abouttwo hours and twenty two minutes. The supported catalyst was recoveredas a light orange, free flowing solid (5.63 g).

Comparative Example 2 Racemicdimethylsiladiyl(2-methyl-4-[1-naphthy]indenyl)₂zirconium dichlorideSupported Comparison Metallocene Catalyst System 2 Racemicdimethylsiladiyl(2-methyl-4-[1-naphthyl]indenyl)₂zirconiumdichloride/MAO

In a 100 mL round bottom flask racemicdimethylsiladiyl(2-methyl-4-[1-naphthy]indenyl)₂ zirconium dichloride(Comparison metallocene 2, 0.064 g) was added to a MAO solution (6.74 g,7.2 mL) and stirred twenty minutes. This was filtered through a mediumglass frit funnel and washed with toluene (14 mL). To the combinedfiltrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600°C. dehydration). This slurry was stirred for twenty minutes then driedat 40° C. for two minutes under vacuum on a rotary evaporator until theliquid evaporated, and then the solid was further dried a total of abouttwo hours. The supported catalyst was recovered as an orange, freeflowing solid (4.72 g).

Example 3 Racemicdimethylsiladiyl-bis-(43′,5′-di-tertbutylphenyl)-2-methylindenyl)zirconiumdichloride 1-bromo-3,5-di-tertbutylbenzene

A 1000 mL three-neck, round-bottom flask was equipped with a mechanicalstirrer, a pressure-compensating dropping funnel, and a refluxcondenser. A nitrogen gas flow adapter with overpressure valve wasattached on top of the reflux condenser. A slight nitrogen flowguaranteed an inert gas atmosphere in the apparatus. The flask wascharged with 181 g triphenylphosphine (690 mmol) and 160 mL acetonitrile(HPLC grade). The white suspension was cooled in an ice bath for 15minutes. While stirring, dropwise addition of 101.5 g bromine (635 mmol)took place within 40 minutes. After bromine addition, the ice bath wasremoved. 124 g of 3,5-di-tertbutylphenol (601 mmol) and 140 mLacetonitrile were added in one portion. The orange/white suspensionconverted into an orange solution upon heating. The mechanical stirrerwas replaced by an egg-shape stir bar. The solution was stirred atgentle reflux temperature for three hours.

The flask was then fitted for a simple distillation and the acetonitrilewas distilled under water aspirator pressure. After all the acetonitrilehad been removed, the condenser was replaced with a short,large-diameter glass tube connected to a 500 mL glass washing bottlehalf filled with water. The liquid mixture was stirred for 80 minutes ata temperature of 280-310° C. The reaction mixture was cooled toapproximately 100° C. and poured into a 1000 mL beaker. A slight flow ofnitrogen into the beaker kept the product mixture dry. At roomtemperature the solid was brought into a dry box, broken into finepieces, and ground in a mortar. The ground material was stirred fourtimes with 200 mL of pentane. The liquid phases were decanted, combined,washed with saturated NaHCO₃ solution (200 mL), dried with MgSO₄, andthe solvent evaporated. Column chromatography (silica/pentane) gave 41.6g (25.7%) of a white, crystalline product.

¹H-NMR (CHCl₃=7.24 ppm): δ 7.30 (s, 3H), 1.28 (s, 18H).

4-(3′,5′-Di-tertbutylphenyl)-2-methylindene

Preparation of the Grignard salt:A 100 ml flask was charged with 1.88 gMg (77.3 mmol) and 10 mL THF. 13.36 g 3,5-di-tertbutyl-bromobenzene(49.6 mmol) were dissolved in 45 mL THF and slowly added to theMg-turnings. The flask was heated to 50° C. in an oil bath as soon asthe reaction started, and this temperature was kept for one hour afteraddition of the bromobenzene was complete. The oil bath temperature wasraised and a gentle reflux maintained for four hours.

Coupling reaction: A 100 mL flask was charged with 7.42 g4-chloro-2-methylindene (45.1 mmol), 0.723 g1,3-bis(diphenylphosphino)propane nickel(II)chloride, (1.334 mmol) and30 mL Et₂O. The red suspension was cooled to −20° C., and theGrignard-salt suspension from above added within 20 minutes. Thesuspension was heated in an oil bath to 50° C., and stirred for 40 hoursat this temperature. The flask was cooled in an ice bath. Whilestirring, 4 ml water and 15 ml 10% aqueous HCl were added. The THF phasewas separated, the water phase washed with Et₂O, and the combinedorganic phases dried with MgSO₄. A purification by column chromatographyfollowed after evaporation of the solvent. Silica was used as thestationary phase and pentane as the solvent. Later the solvent waschanged to a pentane/Et₂O mixture (98:2). All fractions containingproduct were combined, the solvent completely evaporated. The productwas recrystallized in the smallest possible amount of pentane, stored at4° C., the solvent decanted, and the solid dried under vacuum. Yield was3.14 g (9.96 mmol, 21.9%4). The product is a mixture of two isomers

¹H-NMR (CHCl₃=7.24 ppm): δ 7.40-7.12 (m, 2×6H), 6.64 (s, 1H), 6.53 (t,1H), 3.36 (s, 2×2H), 2.13 (s, 2×3H), 1.36 (s, 2×18H).

Dimethylsiladiyl-bis-(4-(3′,5′-di-tertbutylphenyl)-2-methylindene)

3.12 g 4-(3′,5′-Di-tertbutylphenyl)-2-methyl-indene (9.8 mmol) wasdissolved in 20 mL THF. A 100 mL flask was charged with 0.65 g KH and 25mL THF. At a temperature of −75° C. the indene solution was added within8 minutes to the KH suspension. The suspension was allowed to warm upwithin 40 minutes to −50° C., and then within 75 minutes to −35° C.After stirring at room temperature for 90 minutes the solid was allowedto settle, and the orange solution transferred to a second flask. 0.6 mLDichlorodimethylsilane (4.95 mmol) was added to the K-salt solution at−35° C. The solution was stirred overnight at room temperature. Additionof 3 mL saturated NH₄Cl solution stopped the reaction. The solution wasfiltered from a white precipitate and dried with MgSO₄. Addition of 5 gsilica and complete evaporation of solvent gave a silica/raw productmixture. Column chromatography over 125 g silica and pentane/Et₂O=99:1(500 mL) and then 98:2 (500 mL). A quantitative yield with a slightcontamination of indene starting material was recovered. The product isa mixture of two isomers. ¹H-NMR (CHCl₃=7.24 ppm): δ 7.48-7.13 (m,2×12H), 6.80 (m, 2×2H), 3.85 (s, 2H), 3.80 (s, 2H), 2.24 (s, 6H), 2.23(s, 6H), 1.38+1.37 (2s, 2×36H), −0.20 (s, 3H), −0.22 (s, 2×3H), −0.26(s, 3H).

Racemicdimethylsiladiyl-bis-(4-(3′,5′-di-tertbutylphenyl)-2-methyl-indenyl)zirconiumdichloride

4 g of the above silane (5.77 mmol) were dissolved in 6 ml pentane and43 mL THF. At −85° C. 4.6 mL n-BuLi (2.5M in hexanes, 11.5 mmol) wereadded within 11 minutes. The color of the solution turned from yellow tored-brown. The solution was warmed to −60° C. within 30 minutes andstirred at room temperature for one hour. The solvent was completelyevaporated, 10 mL toluene were added, followed again by completeevaporation of the solvent. The red-brown residue was dissolved in 45 mltoluene and cooled to −85° C. Addition of 1.32 g ZrCl₄ (5.66 mmol) gavea brown suspension. Within two hours the suspension was warmed to roomtemperature, and then refluxed for 6.5 hours. This gave a bright orangesuspension. Toluene was completely evaporated, 60 mL pentane were addedto stir the suspension overnight. Filtration over celite and washing ofthe orange residue with 45 mL pentane gave a clear orange filtrate. Byslow evaporation of the pentate solution to the dry box atmosphere, theracemic zirconocene crystallized out of solution. The solution wasdecanted from the solid; the solid washed with a few mL cold pentane anddried. By washing the orange residue on celite above with toluene, aclear orange toluene solution can be obtained. Evaporation of half ofthe toluene and adding at least half the volume of pentane givescrystalline meso zirconocene. Yield of racemic zirconocene was 1.5 g(1.76 mmol, 30.5%). 0.51 g (0.60 mmol, 10.4%) meso zirconocene could beisolated. ¹H-NMR(CHCl₃=7.24 ppm): δ 7.64 (d, 2×1H), 7.51 (s, 4H), 7.40(d, 2×1H), 7.39 (s, 2H), 7.10 (t, 2×1H), 6.95 (s, 2×1H), 2.24 (s, 2×3H),1.33 (s, 2×3H), 1.30 (s, 12×3H) for the racemic zirconocene, and δ0 7.62(d, 2×1H), 7.45 (s, 4H), 7.37 (t, 2×1H), 7.11 (d, 2×1H), 6.86 (m, 2×1H),6.78 (s, 2×1H), 2.44 (s, 2×3H—), 1.46 (s, 3H), 1.31 (s, 12×3H), 1.23 (s,3H) for the meso zirconocene.

Supported Metallocene Catalyst System 3A Racemicdimethylsiladiyl-bis(4-(3′,5′-di-tertbutylphenyl)-2-methylindenyl)zirconiumdichloride/MAO

In a 100 mL round bottom flask racemicdimethylsiladiyl-bis-(4(3′,5′-di-tertbutylphenyl)-2-methylindenyl)zirconium dichloride (0.075 g) was added to a MAO solution (6.74 g, 7.4mL) and stirred twenty minutes. This was filtered through a medium glassfrit funnel and washed with toluene (14 mL). To the combined filtrateswas added dehydrated silica (4.0 g, Davison 948 Regular, 600° C.dehydration). This slurry was stirred for twenty minutes, then dried at40° C. for one minutes under vacuum on a rotary evaporator until theliquid evaporated, and then the solid was further dried a total of abouttwo hours and twenty minutes. The supported catalyst was recovered as areddish pink, free flowing solid (5.4 g).

Dimethylsiladiylbis[4-(3′,5′-di-tert-butylphenyl)-2-methylindenyl]zirconiumdimethyl

Dimethylsiladiylbis[4-(3′,5′-di-tert-butylphenyl)-2-methylindenyl]ZrCl₂(488 mgs, 0.57 mmol) was dissolved in 30 mL of toluene to give a clearorange solution. 3.0M MeMgBr solution in Et₂O (0.76 mL, 2.28 mmol) wasadded at room temperature via syringe and the reaction was stirred atreflux overnight. After this time, the reaction was cooled and 0.5 mL of1,4-dioxane and 0.5 mL of Me₃SiCl was added to the solution. Thissolution was filtered through a celite-packed frit and the toluene wasremoved in vacuo. The remaining yellow solid was washed with pentane anddried in vacuo to yield 257 mgs (55.3%) of the desired metallocene.

Supported Metallocene Catalyst System 3B Racemicdimethylsiladiyl-bis-(4-(3′,5′-di-tertbutylphenyl)₂-methylindenyl)zirconiumdimethyl/NCA

In a 50-ml beaker, 1.07 g (0.232 mmol) of an 11.05 wt % solution of tris(perfluorophenyl) borane in toluene was massed. 0.035 g (0.232 mmol) ofN,N-diethylaniline (Aldrich, 98+%) was added followed by 4.5 g oftoluene. A pink solution resulted. This solution was pipetted into a 50ml round bottom flask containing 2.0 g of silica (Grace Davison,calcined at 500° C. with 3-wt % (NH₄)₂SiF₆) and a magnetic stir bar. 4.5g of toluene was used to rinse the beaker, pipette, and the sides of theflask. The flask was heated to 50° C. in an oil bath. The mixture wasstirred for 30 minutes. 0.023 g (0.028 mmol) of the dimethylsiladiyl-bis-(4-(3′,5′-di-tertbutylphenyl)₂-methylindenyl) zirconium dimethyl wasadded as a solid to produce a red slurry. Stirring was continued for 1hour at 50° C. After this time, the stirring and heating werediscontinued. The solvent was stripped overnight in vacuo to give 2.13 gof a flesh colored powder. Composition by mass balance: Zirconium: 0.013mmol/g catalyst, Boron: 0.11 mmol/g catalyst.

Supported Metallocene Catalyst System 3C Racemicdimethylsiladiyl-bis-(4-(3′,5′-di-tertbutylphenyl)₂-methylindenyl)zirconiumdimethyl/NCA

This catalyst preparation used the same raw materials as above. In a 50mL beaker, 2.68 g (0.58 mmol) of an 11.05-wt/o solution of tris(perfluorophenyl) borane in toluene was massed. 0.088 g (0.59 mmol) ofN, N-diethylaniline was added followed by 15 g of toluene. A pinksolution resulted. This solution was pipetted into a 100 mL round bottomflask containing 5.0 g of silica and a magnetic stir bar. 1.0 g oftoluene was used to rinse the beaker, pipette, and the sides of theflask. The flask was heated to 50° C. in an oil bath. The mixture wasstirred for 30 minutes. 0.0061 g (0.075 mmol) of thedimethylsiladiyl-bis-(4(3′,5′ di-tertbutylphenyl)-2-methylindenyl)zirconium dimethyl was added as a solid to produce a red slurry.Stirring was continued for 30 minutes at 50° C. After this time, thestirring and heating were discontinued. The solvent was strippedovernight in vacuo to give 5.36 g of a flesh colored powder. Compositionby mass balance: Zr: 0.013 mmol/g catalyst, B: 0.11 mmol/g catalyst.

Example 4 Racemic[9-Silafluorenebis(4-(3′,5′-di-t-butylphenyl)-2-methylindene]zirconiumdichloride 4-[3′,5′-di-t-butylphenyl]-2-methylindene

4-Chloro-2-methylindene (6.1 g, 37 mmol) and NiCl₂(PPh₃)₂ (1.8 g, 2.8mmol) were dissolved in 150 mL of Et₂O. 3,5-Di-t-butylphenylmagnesiumbromide (10 g, 37 mmol) as a Et₂O solution was added to the solution andthe reaction was stirred overnight at room temperature. After overnightstirring, the reaction was slowly quenched with H₂O to neutralizeunreacted Grignard. The solution was subsequently treated with 100 mL of10% HCl(aq), neutralized with saturated sodium bicarbonate aqueoussolution. The organic layer was dried with magnesium sulfate and thesolvent was removed by rotary evaporation. The remaining residue wasloaded onto a silica gel column and eluted with hexane. Yield was 4.6 g(40%).

Lithium 4-[3′,5′-di-t-butylphenyl]-2-methyl indene

4-[3′,5′-Di-t-butylphenyl]-2-methylindene (4.7 g, 15 mmol) was dissolvedin 80 mL of pentane. To this solution was added 5.9 mL of n-BuLi (2.5Min hexane) and the reaction is allowed to stir 4 hours at roomtemperature. A white solid precipitated from solution and was collectedby frit filtration and washed with additional pentane. Yield was 3.6 g(78%).

9-silafluorenebis[4-(3′,5′-di-t-butylphenyl)-2-methylindene

9,9-Dichloro-9-silafluorene (1.2 g, 9.2 mmol) was dissolved in 80 mL ofTHF. To this solution was slowly added lithium4(3′,5′-di-t-butylphenyl)-2-methylindene (3.0 g, 9.2 mmol) as a drypowder and the solution was stirred overnight. After this time, thesolvent was removed in vacuo and the residue was taken up in diethylether. The solution was filtered through a frit to remove LiCl and thesolvent was removed in vacuo and used as a crude product (4.1 g) for thenext step.

[9-silafluorenebis(4-(3′,5′-di-t-butylphenyl)-2-methylindene]ZrCl₂

The crude solid from the previous step (4.1 g, 5.5 mmol) was taken up in50 mL of diethyl ether. To this solution was slowly added n-BuLi (4.4mL, 2.5 M in hexane) and stirred for 3 hours at room temperature. Thesolution was cooled to −30° C. and ZrCl₄ (1.28 g, 4.6 mmol) was added asa dry powder and stirred at room temperature for two hours. The solventwas removed in vacuo and toluene as added to the crude residue. Thesolution was filtered to remove LiCl. The filtrate was concentrated andpentane is added under heating. The solution was cooled to inducecrystallization. Yield of pure racemic isomer was 187 mgs (3.7%).

Supported Metallocene Catalyst System 4 Racemic[9-silafluorenebis(4(3′,5′-di-t-butylphenyl)-2-methylindene]zirconiumdichloride

In a 100 mL round bottom flask racemic[9-Silafluorenebis(4-(3′,5′-di-t-butylphenyl)₂-methylindene]zirconiumdichloride (0.085 g) was added to a MAO solution (6.74 g, 7.2 mL) andstirred twenty minutes. This was filtered through a medium glass fritfunnel and washed with toluene (14 mL). To the combined filtrates wasadded dehydrated silica (4.0 g, Davison 948 Regular, 600° C.dehydration). This slurry was stirred for twenty minutes, then dried at40° C. for two minutes under vacuum on a rotary evaporator until theliquid evaporated, and then the solid was further dried a total of abouttwo hours and twenty minutes. The supported catalyst was recovered as apink reddish, free flowing solid (5.24 g).

Example 5 Racemic[9-silafluorenebis(4(3′,5′-di-t-butylphenyl)-2-isopropylindene]zirconiumdichloride 4-[3′,5′-di-1-butylphenyl]-2-isopropylindene

4-Chloro-2-isopropylindene (7.2 g, 37 mmol) and NiCl₂(PPh₃)₂ (1.8 g, 2.8mmol) were dissolved in 150 mL of Et₂O. 3,5-Di-di-t-butylphenylmagnesiumbromide (10 g, 37 mmol) as a Et₂O solution was added to the solution andthe reaction was stirred overnight at room temperature. After overnightstirring, the reaction was slowly quenched with H₂O to neutralizeunreacted Grignard. The solution was subsequently treated with 100 mL of10% HCl(aq), neutralized with saturated sodium bicarbonate aqueoussolution. The organic layer was dried with magnesium sulfate and thesolvent was removed by rotary evaporation. The remaining residue wasloaded onto a silica gel column and eluted with hexane. Yield is 5.8 g(45%).

Lithium 4-[3′,5′-di-t-butylphenyl]-2-isopropylindene

4-[3′,5′-di-t-butylphenyl]-2-isopropylindene (5.8 g, 17 mmol) wasdissolved in 80 mL of pentane. To this solution was added 6.6 mL ofn-BuLi (2.5M in hexane) and the reaction was allowed to stir 4 hours atroom temperature. A white solid precipitated from solution and wascollected by frit funnel filtration and washed with additional pentane.Yield is 5.0 g (87%).

Silafluorenebis[4-(3′,5′-bis-[t-butyl]phenyl)2-isopropylindene

9,9-Dichloro-9-silafluorene (1.1 g, 8.5 mmol) was dissolved in 80 mL ofTHF. To this solution was slowly added lithium4-(3′,5′-di-t-butylphenyl)-2-isopropylindene (3.0 g, 1.5 mmol) as a drypowder and the solution was stirred overnight. After this time, thesolvent was removed in vacuo and the residue was taken up in diethylether. The solution as filtered through frit to remove LiC and thesolvent was removed in vacuo and used as a crude product (3.9 g) for thenext step.

9-silafluorenebis(4-(3′,5′-di-t-butylphenyl)-2-isopropylindene]ZrCl₂

The crude solid from the previous step (3.9 g, 4.6 mmol) was taken up in50 mL of diethyl ether. To this solution was slowly added n-BuLi (3.7mL, 2.5 M in hexane) and stirred for 3 hours at room temperature. Thesolution was cooled to −30° C. and ZrCl₄ (1.1 g, 4.6 mmol) was added asa dry powder and stirred at room temperature for two hours. The sol ventwas re moved in vacuo and toluene was added to the crude residue. Thesolution was filtered to remove LiCl. The filtrate was concentrated andpentane added under heating. The solution was cooled to inducecrystallization. Yield of pure racemic isomer was 280 mgs (6.0%).

Supported Metallocene Catalyst System 5 Racemic[9-silafluorenebis(4-(3′,5′-di-t-butylphenyl)-2-isopropylindene]zirconiumdichloride

In a 100 mL round bottom flask racemic[[9-Silafluorenebis(4-(3′,5′-di-t-butylphenyl)-2-isopropylindene]zirconiumdichloride (0.090 g) was added to a MAO solution (6.74 g, 7.2 mL) andstirred twenty minutes. This was filtered through a medium glass fritfunnel and washed with toluene (14 mL). To the combined filtrates wasadded dehydrated silica (4.0 g, Davison 948 Regular, 600° C.dehydration). This slurry was stirred for twenty minutes, then dried at40° C. for two minutes under vacuum on a rotary evaporator until theliquid evaporated and then the solid was further dried a total of abouttwo hours and twenty minutes. The supported catalyst was recovered as alight purple, free flowing solid (5.17 g).

Example 6Dimethylsiladiyl-bis-(2-methyl-4-(3′,5′-di-methylphenyl)indenyl)zirconium dichloride 4-(3′,5′-dimethylphenyl)-2-methylindene

4-Chloro-2-methylindene (8.9 g, 54 mmol) and NiCl₂(PPh₃)₂ (1.8 g, 2.8mmol) were dissolved in 150 mL of Et₂O. 3,5-Dimethylphenylmagnesiumbromide (10 g, 54 mmol) as a Et₂O solution was added to the solution andthe reaction was stirred overnight at room temperature. After overnightstirring, the reaction was slowly quenched with H₂O to neutralizeunreacted Grignard. The solution was subsequently treated with 100 mL of10% HCl(aq), neutralized with saturated sodium bicarbonate aqueoussolution. The organic layer was dried with magnesium sulfate and thesolvent was removed by rotary evaporation. The remaining residue wasloaded onto a silica gel column and eluted with hexane. Yield was 5.6 g(44%).

Lithium 4-(3′,5′-dimethylphenyl)-2-methylindene

4-(3′,5′-dimethylphenyl)-2-methylindene (5.6 g, 23.9 mmol) was dissolvedin 80 mL of pentane. To this solution was added 9.6 μL of n-BuLi (2.5Min hexane) and the reaction was allowed to stir 4 hours at roomtemperature. A white solid precipitated from solution and was collectedby frit filtration and washed with additional pentane. Yield was 4.5 g(80%).

Dimethylsilylbis[4-(3′,5′-dimethylphenyl)-2-methylindene

SiMe₂Cl₂ (1.2 g, 9.4 mmol) was dissolved in 80 mL of THF. Whilestirring, lithium 4-(3,5-dimethylphenyl)-2-methylindenide (4.5 g, 18.7mmol) was added as a dry powder and the contents were allowed to stirovernight at room temperature. The solvent was removed in vacuo and theresidue was taken up in pentane and filtered to remove LiCl salts. Thepentane was removed in vacuo to yield a flaky white solid (4.23 g, 87%).

Dimethylsiladiylbis[4-(3′,5′-dimethylphenyl)-2-methylindene]ZrCl₂

Dimethylsilylbis[4-(3′,5′-dimethylphenyl)-2-methylindene] (4.23 g, 8.0mmol) was dissolved in 60 mL of Et₂O. While stirring, 6.4 mL of n-BuLi(2.5M in hexane) was added and allowed to stir at room temperature fortwo hours. After this time, the solution was cooled to −35° C. and ZrCl₄(1.58 g, 8.0 mmol) was added and allowed to stir at room temperature for3 hours. The solvent was then removed in vacuo and the residue was takenup in a mixture of methylene chloride and pentane and filtered to removeLiCl salts. The filtrate was then concentrated and chilled to −35° C. toinduce crystallization. 0.23 g (5.0%) of pure racemic compound wasobtained.

Supported Metallocene Catalyst System 6Dimethylsiladiyl-bis-(2-methyl-4(3′,5′-di-methylphenyl)indenyl)zirconiumdichloride/MAO

In a 100 mL round bottom flaskDimethylsiladiyl-bis-(2-methyl-43′,5′-di-methylphenyl)indenyl) zirconiumdichloride (0.061 g) was added to a MAO solution (6.74 g, 7.4 mL) andstirred twenty minutes. This was filtered through a medium glass fritfunnel and washed with toluene (14 mL). To the combined filtrates wasadded dehydrated silica (4.0 g, Davison 948 Regular, 600° C.dehydration). This slurry was stirred for twenty minutes, then dried at40° C. for two minutes under vacuum on a rotary evaporator until theliquid evaporated, and then the solid was dried a total of about twohours and thirty four minutes. The supported catalyst was recovered as alight orange, free flowing solid (5.36 g).

Example 7Dimethylsiladiyl-bis-(4(3′,5′-bistrifluoromethylphenyl)-2-methyl-indenyl)zirconiumdichloride 4-[3′,5′-bis(trifluoromethyl)phenyl]-2-methylindene

4-Bromo-2-methylindene (10.7 g, 51 mmol) and NiCl₂(PPh₃)₂ (1.8 g, 2.8mmol) were dissolved in 150 mL of Et₂O.3,5-bis(trifluoromethyl)phenylmagnesium bromide (51 mmol) as a Et₂Osolution was added under vigorous stirring and the reaction stirredovernight at room temperature. After overnight stirring, the reactionwas slowly quenched with H₂O to neutralize unreacted Grignard. Thesolution was subsequently treated with 100 mL of 10% HCl(aq), andneutralized with saturated sodium bicarbonate aqueous solution. Theorganic layer was dried with magnesium sulfate and the solvent wasremoved by rotary evaporation. The remaining residue was loaded onto asilica gel column and eluted with hexane. Yield was 2.2 g (13%).

Lithium 4-[3′,5′-bis(trifluoromethyl) phenyl]-2-methylindenide

4-[3′,5′-bis(trifluoromethyl) phenyl]-2-methylindene (2.2 g, 675 mmol)was dissolved in 50 mL of pentane. To this solution was added 2.6 mL ofn-BuLi (2.5M in hexane) and the reaction was allowed to stir 4 hours atroom temperature. A yellow-white solid precipitated from solution andwas collected by frit filtration and washed with additional pentane.Yield was 1.6 g (73%).

Dimethylsiladiylbis[4-(3′,5′-bis[trifluoromethyl]phenyl)-2-methylindene

SiMe₂Cl₂ (0.48 g, 3.7 mmol) was dissolved in 80 mL of THF. Whilestirring, lithium 4-[3′,5′-bis(trifluoromethylphenyl]-2-methylindenide(2.6 g, 7.5 mmol) was added as a dry powder and the contents wereallowed to stir overnight at room temperature. The solvent was removedin vacuo and the residue taken up in pentane and filtered to remove LiClsalts. The pentane was removed in vacuo, and the crude product is loadedonto a silica gel column and eluted with hexane. Yield was 2.2 g (80%)

Dimethylsiladiylbis[4-(3′,5′-bis[trifluoromethyl]phenyl)-2-methylindene]ZrCl₂

Dimethylsiladiylbis[4-(3′,5′-bis[trifluoromethylphenyl])-2-methylindene](2.2 g, 3.0 mmol) was dissolved in 50 mL of Et₂O. While stirring, 2.4 mLof n-BuLi (2.5M in hexane) was added and allowed to stir at roomtemperature for two hours. After this time, the solution was cooled to−35° C. and ZrCl₄ (0.69 g, 3.0 mmol) was added and allowed to stir atroom temperature for 3 hours. The solvent was then removed in vacuo andthe residue taken up in toluene and filtered to remove LiCl salts. Thefiltrate was then concentrated and chilled to −35° C. to inducecrystallization. 90 mg (3.3%) of pure racemic compound was obtained.

Supported Metallocene Catalyst System 7Dimethylsiladiyl-bis-(4-(3′,5′-bistrifluoromethylphenyl)-2-methyl-indenyl)zirconiumdichloride MAO

In a 100 mL round bottom flaskdimethylsiladiyl-bis-(4-(3′,5′-bistrifluoromethylphenyl)-2-methyl-indenyl)zirconiumdichloride (0.075 g) was added to a MAO solution (6.32 g, 6.75 mL) andstirred twenty minutes. This was filtered through a medium glass fritfunnel and washed with toluene (13 mL). To the combined filtrates wasadded dehydrated silica (3.75 g, Davison 948 Regular, 600° C.dehydration). This slurry was stirred for thirty minutes then dried at40° C. for two minutes under vacuum on a rotary evaporator until theliquid evaporated and then the solid was further dried a total of abouttwo hours and twenty minutes. The supported catalyst was recovered as adull red pink, free flowing solid (5.03 g).

Example 8Dimethylsiladiylbis(4(3′,5′-bis-trimethylsilyl-phenyl)-2-methylindenyl)zirconiumdichloride 3.5-Dibromo-trimethylsilyl-benzene

42.4 g of Tribromobenzene (134.6 mmol) was dissolved in 600 mL Et₂O. Thesolution was chilled to −55° C., at which temperature starting materialprecipitated. 54 mL of n-BuLi (2.5 M in hexanes, 135 mmol) were addedwithin 20 minutes. After stirring for 35 minutes at −52° C., 20 ml TMSCl(158 mmol) and 20 mL Et₂O were added within 7 minutes. The suspensionturned into a solution at 42° C., and a fine precipitate appeared at−30° C. The suspension was stirred overnight at room temperature. 100 mL2M HCl were used to hydrolyze the mixture. After stirring for 30minutes, the Et₂O-phase was dried with MgSO₄, filtered, and solventevaporated until compound crystallized out of solution. The flask wasstored overnight at +4° C. The crystalline compound was filtered, washedwith a small amount cold pentane, and dried under vacuo. A secondfraction of crystalline compound was obtained from the filtrate. Yield:31.9 g (103.5 mmol, 77%). ¹H-NMR (CHCl₃=7.24 ppm): δ 7.62 (t, 1H), 7.49(d, 2H), 0.25 (s, 3×3H).

3,5-Bis-trimethylsilyl-bromobenzene

17.18 g of 3,5-Dibromo-trimethylsilyl-benzene, 55.8 mmol, was dissolvedin 380 ml Et₂O. The solution was chilled to −68° C., and 22.3 mL ofn-BuLi (2.5 M in hexanes), 55.8 mmol, were added within 18 minutes. Thesolution changed its color from clear to yellow, and was stirred for 45minutes at −68° C. 7.5 mL TMSCl, 59 mmol, were added within six minutes.The temperature of solution rose within one hour to −33° C., and afteranother 30 minutes to −18° C. The solution was stirred overnight at roomtemperature. 60 mL of 2M HCl were added to the white suspension.Stirring for 30 minutes resulted in two clear phases. Et₂O-phase wasdried with MgSO₄, filtered, and solvent evaporated. Raw product wasdistilled at a temperature of 70-76° C. and 0.1-0.2 mbar. All purefractions were combined and gave 15.8 g of product (52.4 mmol, 94%).¹H-NMR (CHCl₃=7.24 ppm): δ 7.56 (s, 2H), 7.50 (t, 1H), 0.25 (s, 6×3H).

4-(3′,5′-Bis-trimethylsilyl-phenyl)-2-methylindene

Preparation of the Grignard salt: A 100 mL flask was charged with 2.9 gMg (119 mmol) and 10 ml THF. 15.8 g 3,5-Bis-trimethylsilyl-bromobenzene(52.4 mmol) were dissolved in 45 mL THF and slowly added to theMg-turnings at room temperature. The reaction started after 5 minutesresulting in a black-brown, hot solution. The mixture was stirredovernight, maintaining a gentle reflux temperature.

Coupling reaction: A 100 mL flask was charged with 8.2 g4-chloro-2-methylindene (49.8 mmol) and 1.14 g1,2-bis(diphenylphosphino)ethane nickel(II)chloride (2.16 mmol). At roomtemperature the Grignard-salt suspension from above was poured to theindene/nickel catalyst suspension. The suspension was stirred for 16hours at gentle reflux temperature. While stirring, 5 ml water and 10 mL10% aqueous HCl were added. The THF phase was separated, the water phasewashed with Et₂O, and the combined organic phases dried with MgSO₄.Purification by column chromatography followed after evaporation of thesolvent. Silica was used as the stationary phase and pentane as thesolvent. Later the solvent was changed to a pentane/Et₂O mixture (98:2).All fractions containing product were combined, the solvent completelyevaporated. Yield was 15.35 g, 43.8 mmol (83.5%). The product is amixture of two diastereomers. ¹H-NMR (CHCl₃=7.24 ppm): δ 7.67-7.63 (m,2×3H), 7.37-7.10 (m, 2×3H), 6.61 (s, 1H), 6.53 (d, 1H), 3.36 (s, 2H),3.34 (s, 2H), 2.13 (s, 2×3H), 0.29 (s, 2×18H).

Dimethylsiladiylbis(4-(3′,5′-bis-trimethylsilyl-phenyl)-2-methylindene)

15.35 g 4-(3′,5′-Bis-trimethylsilyl-phenyl)-2-methyl-indene (43.8 mmol)were dissolved in 70 mL THF. A second flask was charged with 2.6 g KH,and 70 mL THF. At a temperature of −65° C. the indene solution was addedwithin 20 minutes to the KH suspension. After stirring at roomtemperature for two hours the solid was allowed to settle for 30minutes, and the red solution transferred to a new flask. A few ml THFwere added to the KH suspension, let stir and settle, and transferredalso this solution to the new flask. 2.6 mL Dimethyldichlorosilane (21.4mmol) were added to the K-salt solution at −35° C. The solution wasstirred over night at room temperature. Addition of 10 ml sat. NH₄Clsolution stopped the reaction. The solution was filtered from a whiteprecipitate, and dried with MgSO₄. Addition of 22 g silica and completeevaporation of solvent gave a silica/raw product mixture. Columnchromatography was done over 250 g silica with pentane/Et₂O mixtures of99:1 to 96:4. Obtained were 11.2 g product (14.79 mmol, 67.5%), and 2.7g of a less pure fraction. The product is a mixture of two isomers.¹H-NMR (CHCl₃=7.24 ppm): δ 7.68-7.14 (m, 2×12H), 6.78 (m, 2×2H), 3.85(s, 2H), 3.81 (s, 2H), 2.24 (s, 6H), 2.23 (s, 6H), 0.31 (2s, 2×36H),−0.19 (s, 3H), −0.23 (s, 3H), −0.26 (s, 6H).

Dimethylsiladiylbis(4-(3′,5′-bis-trimethylsilyl-phenyl)-2-methylindenyl)zirconium dichloride

4.1 g Silane from above (5.4 mmol) were dissolved in 50 mL THF. At acooling bath temperature of −83° C., 4.3 mL n-BuLi (2.5M in hexanes,10.8 mmol) were added within one minute. The color of the solutionturned from yellow to red-brown. The solution was warmed to −30° C.within 100 minutes and then stirred at room temperature for 100 minutes.The solvent was completely evaporated, 13 mL toluene were addedfollowing again complete evaporation of the solvent. The residue wasdissolved in 50 ml toluene and cooled to −82° C. Addition of 1.26 gZrCl₂ (5.41 mmol) resulted in a light brown suspension. The suspensionwas stirred overnight at room temperature, refluxed for 5.5 hours, andagain stirred overnight at room temperature. This resulted in an orangesuspension. Filtration over celite and complete evaporation of toluenegave an orange solid. 40 mL Pentane was added to the solid, and thesuspension stirred. Filtration, using a frit, washing with 3 mL coldpentane, and drying under vacuo gave fraction 1 (1.56 g). Rac/meso ratioof fraction 1 is 8:92. All solvent was evaporated from the filtrate, andexactly 8 mL pentane were added to dissolve the residue. The solutionwas placed in a freezer at −35° C. which initiated the crystallizationof a solid compound. Filtration, using a frit, washing with a few mLcold pentane, and drying under vacuo gave fraction 2 (0.63 g). Rac/mesoratio of fraction 2 is 85:15. All solvent was evaporated from thefiltrate, and the solid kept as fraction 3 (1.77 g). Rac/meso ratio offraction 3 is 73:27. ¹H-NMR (CHCl₃=7.24 ppm): δ 7.78 (s, 2×2H), 7.70 (d,2×1H), 7.64 (s, 2×1H), 7.41 (d, 2×1H), 7.12 (m, 2×1H), 6.91 (s, 2×1H),2.25 (s, 2×3H), 1.32 (s, 2×3H), 0.24 (s, 12×3H) for the racemiczirconocene, and δ 7.72 (s, 2×2H), 7.66 (s, 2×1H), 7.62 (s, 2×1H), 7.12(d, 2×1H), 6.88 (m, 2×1H), 6.75 (s, 2×1H), 2.43 (s, 2×3H), 1.46 (s, 3H),1.23 (s, 3H), 0.25 (s, 12×3H) for the meso zirconocene.

Supported Metallocene Catalyst System 8Dimethylsiladiylbis(4-(3′,5′-bis-trimethylsilylphenyl)-2-methylindenyl)zirconiumdichloride/MAO

In a 100 mL round bottom flaskDimethylsiladiylbis(43′,5′-bis-trimethylsilyl-phenyl)-2-methylindenyl)zirconium dichloride (0.080 g) was added to a MAO solution (6.74 g, 7.3mL) and stirred twenty minutes. This was filtered through a medium glassfrit funnel and washed with toluene (14 mL). To the combined filtrateswas added dehydrated silica (4.0 g, Davison 948 Regular, 600° C.dehydration). This slurry was stirred for twenty minutes, then dried at40° C. for two minutes under vacuum on a rotary evaporator until theliquid evaporated, and then the solid was further dried a total of about4 hours and thirty minutes. The supported catalyst was recovered as apink red, free flowing solid (5.15 g).

Example 9 Dimethylsiladiylbis[4-(3′,5′-dimethylphenyl)-2isopropylindene]zirconium dichloride4(3′,5′-dimethylphenyl)-2-isopropylindene

4-chloro-2-isopropylindene (10.0 g, 54 mmol) and NiCl₂(PPh₃)₂ (1.8 g,2.8 mmol) were dissolved in 150 mL of Et₂O. 3,5-dimethylphenylmagnesiumbromide (54 mmol) as a Et₂O solution was added under vigorous stirringand the reaction was stirred overnight at room temperature. Afterovernight stirring, the reaction was slowly quenched with H₂O toneutralize unreacted Grignard. The solution was subsequently treatedwith 100 mL of 10% HCl(aq), neutralized with saturated sodiumbicarbonate aqueous solution. The organic layer was dried with magnesiumsulfate and the solvent was removed by rotary evaporation. The remainingresidue was loaded onto a silica gel column and eluted with hexane.Yield was 5.5 g (39%).

Lithium 4-(3′,5′-dimethylphenyl),2-isopropylindenide

4-(3′,5′-dimethylphenyl)-2-isopropylindene (5.5 g, 21 mmol) wasdissolved in 80 mL of pentane. To this solution was added 8.3 mL ofn-BuLi (2.5M in hexane) and the reaction was allowed to stir 4 hours atroom temperature. A white solid precipitated from solution and wascollected by frit filtration and washed with additional pentane. Yieldwas 3.3 g (60%).

Dimethylsiladiylbis[4-(3′,5′-dimethylphenyl),2-isopropylindene

SiMe₂Cl₂ (0.69 g, 5.4 mmol) was dissolved in 80 mL of THF. Whilestirring, lithium 4-(3′,5′-dimethylphenyl)-2-isopropylindenide (2.9 g,11 mmol) was added as a dry powder and the contents allowed to stirovernight at room temperature. The solvent was removed in vacuo and theresidue was taken up in pentane and filtered to removed LiCl salts. Thepentane was removed in vacuo to yield a flaky white solid (2.1 g, 67%)

Dimethylsiladiylbis[4-(3′,5′-dimethylphenyl)-2-isopropylindene]ZrCl₂

Dimethylsiladiylbis[4-(3′,5′-dimethylphenyl)-2-isopropylindene] (2.1 g,3.6 mmol) was dissolved in 60 mL of Et₂O. While stirring, 2.9 mL ofn-BuLi (2.5M in hexane) was added and allowed to stir at roomtemperature for two hours. After this time, the solution was cooled to−35° C. and ZrCl₄ (0.83 g, 3.6 mmol) was added and allowed to stir atroom temperature for 3 hours. The solvent was then removed in vacuo andthe residue taken up in toluene and filtered to remove LiCl salts. Thefiltrate was then concentrated and chilled to −35° C. to inducecrystallization. 0.24 g (6.0%) of pure racemic compound was obtained.

Supported Metallocene Catalyst System 9Dimethylsiladiylbis[4-(3′,5′-dimethylphenyl)-2-isopropylindene]zirconiumdichloride/MAO

In a 100 mL round bottom flaskdimethylsiladiylbis[4(3′,5′-dimethylphenyl)-2-isopropylindene)zirconiumdichloride (0.066 g) was added to the MAO solution (6.74 g, 7.2 mL) andstirred twenty minutes. This was filtered through a medium glass fritfunnel and washed with toluene (14 mL). To the combined filtrates wasadded dehydrated silica (4.0 g, Davison 948 Regular, 600° C.dehydration). This slurry was stirred for twenty minutes, then dried at40° C. for two minutes under vacuum on a rotary evaporator until theliquid evaporated, and then the solid was further dried a total of abouttwo hours and thirty minutes. The supported catalyst was recovered as apurple, free flowing solid (5.11 g).

Example 10[9-silafluorenebis(4-(3′,5′-dimethylphenyl)-2-isopropylindene]zirconiumdichloride 2,2′-Dibromobiphenyl

To a stirred solution of o-dibromobenzene (47.3 g, 0.2 mol) in 450 mL ofanhydrous THF was added 76.4 mL of n-BuLi (1.0M in Et₂O). Theo-dibromobenzene solution was cooled in a dry ice/acetone bath. Theyellow-green reaction mixture was allowed to warm to 5° C. and was thenhydrolyzed with 100 mL of 5% hydrochloric acid. The resulting layerswere separated and the aqueous layer extracted 4 times with 4×20 mLportions of diethyl ether. The ether washings were combined with theoriginal organic layer, the whole was dried over sodium sulfate,filtered, and concentrated by distillation until the distillationtemperature reached 70° C. The residue was treated with 50 mL ofabsolute ethanol and cooled to give 2,2′-dibromobiphenyl. Yield was 2.32g (7.4%)

9,9-Dichloro-9-silafluorene

Lithium wire (3.33 g, 0.08 mol) was washed with pentane, carefully cutinto small pieces, and suspended in 150 mL of Et₂O. While stirring,2,2-dibromobiphenyl (25 g, 0.08 mol) 100 mL of diethyl ether was addeddropwise over 1 hour and the contents were allowed to stir for 10 hours.The mixture was filtered through a flit to remove any unreacted Li andLiBr. The filtrated was loaded into an addition funnel and slowlydropped into a solution containing SiCl₄ (50 g, 0.08 mol) in 200 mL ofEt₂O. After addition, the contents were stirred at room temperature for5 hours. The solvent was removed in vacuo and 300 mL of pentane wasadded. The solution was filtered to remove LiCl and the solvents wereagain removed in vacuo. The solids were then loaded into a sublimatorand allowed to sublime at 150° C. under full vacuum. Yield was 10.0 g(51%).

4-(3′,5′-dimethylphenyl)-2-isopropylindene

4-chloro-2-isopropylindene (10 g, 54 mmol) and NiCl₂(PPh₃)₂ (1.8 g, 2.8mmol) were dissolved in 150 mL of Et₂O. 3,5-Dimethylphenylmagnesiumbromide (54 mmol) as a Et₂O solution was added under vigorous stirringand the reaction was stirred overnight at room temperature. Afterovernight stirring, the reaction was slowly quenched with H₂O toneutralize unreacted Grignard. The solution was subsequently treatedwith 100 mL of 10% HCl(aq) neutralized with saturated sodium bicarbonateaqueous solution. The organic layer was dried with magnesium sulfate andthe solvent was removed by rotary evaporation. The remaining residue wasloaded onto a silica gel column and eluted with hexane. Yield was 5.5 g(39%)

Lithium 4-(3′,5′-dimethylphenyl)₂-isopropylindene

4-(3′,5′-dimethylphenyl)-2-methylindene (5.6 g, 24 mmol) was dissolvedin 80 mL of pentane. To this solution was added 9.6 mL of n-BuLi (2.5Min hexane) and the reaction was allowed to stir 4 hours at roomtemperature. A white solid precipitated from solution and was collectedby frit filtration and washed with additional pentane. Yield was 4.5 g(80%).

9-silafluorenebis(4-(3′,5′-dimethylphenyl)-2-isopropylindene

9,9-dichloro-9-silafluorene (1.4 g, 11 mmol) was dissolved in 80 mL ofTHF. To this solution was slowly added lithium4-(3′,5′-dimethylphenyl)-2-methylindene (3.0 g, 11 mmol) as a dry powderand the solution was stirred overnight. After this time, the solvent wasremoved in vacuo and the residue was taken up in diethyl ether. Thesolution was filtered through flit to remove LiCl and the solvent wasremoved in vacuo and used as a crude product (2.1 g) for the next step.

[9-silafluorenebis(4(3′,5′-dimethylphenyl)-2-isopropylindene]ZrCl₂

The crude solid from the previous step (2.1 g, 3.2 mmol) was taken up in50 mL of diethyl ether. To this solution was slowly added n-BuLi (2.56mL, 2.5 M in hexane) and then stirred for 3 hours at room temperature.The solution was cooled to −30° C. and ZrCl₄ (0.74 g, 3.2 mmol) wasadded as a dry powder and stirred at room temperature for two hours. Thesolvent was removed in vacuo and toluene was added to the crude residue.The solution was filtered to remove LiCl. The filtrate was concentratedand pentane was added under heating. The solution was cooled to inducecrystallization. Yield of pure rac/meso metallocene was 120 mgs (3.8%).

Supported Metallocene Catalyst System 10 Rac/meso[9-silafluorenebis(4-(3′,5′-dimethylphenyl)-2-isopropylindene]zirconiumdichloride/MAO

In a 100 mL round bottom flask rac/meso[9-silafluorenebis(43′,5′-dimethylphenyl)-2-isopropylindene]zirconiumdichloride (0.076 g) was added to the MAO solution (6.74 g, 7.2 mL) andstirred twenty minutes. This was filtered through a medium glass fritfunnel and washed with toluene (14 mL). To the combined filtrates wasadded dehydrated silica (4.0 g, Davison 948 Regular, 600° C.dehydration). This slurry was stirred for twenty minutes, then dried at40° C. for two minutes under vacuum on a rotary evaporator until theliquid evaporated, and then the solid was further dried a total of abouttwo hours and thirty minutes. The supported catalyst was recovered as adull purple, free flowing solid (5.06 g).

Polymerizations Isotactic Polypropylene Homopolymer

The polymerization procedure for producing homopolymers with thesupported catalyst systems prepared as described above was as follows.In a clean, dry two liter autoclave which had been flushed withpropylene vapor, TEAL scavenger (0.3 mL, 1.5M) was added. Hydrogen gaswas added at this point if indicated. The quantity of hydrogen is 1.55millimoles for each psi added as shown in the Tables. The reactor wasclosed and filled with 800 mL liquid propylene. After heating thereactor to the indicated polymerization temperature, the catalyst wasadded by washing in with propylene (200 mL). After the indicated time,typically one hour, the reactor was cooled, and the excess propylenevented. The polymer was removed and dried.

Random copolymer (RCP)

The polymerization procedure for producing random copolymers with thesupported catalyst systems prepared as described above was as follows.In a clean, dry two liter autoclave which had been flushed withpropylene vapor, TEAL scavenger (0.3 mL, 1.5M) was added. Hydrogen gaswas added at this point if indicated. The quantity of hydrogen is 1.55millimoles for each psi added as shown in the Tables. The reactor wasclosed and filled with 800 mL liquid propylene. After heating thereactor to 60° C., a partial pressure of ethylene was added as indicatedand then the catalyst was added by washing in with propylene (200 mL).Ethylene gas was fed to maintain a constant pressure. After theindicated time, typically one hour, the reactor was cooled, and theexcess propylene and ethylene vented. The polymer was removed and dried.

Impact Copolymers (ICP)

The polymerization procedure for producing ICP with the supportedcatalyst systems prepared as described above was as follows. In a clean,dry two liter autoclave which had been flushed with propylene vapor,TEAL scavenger (0.3 mL, 1.5M) was added. Hydrogen gas was added at thispoint. The quantity of hydrogen is 1.55 millimoles for each psi added asshown in the Tables. The reactor was closed and filled with 800 mLliquid propylene. After heating the reactor to 70° C., the catalyst wasadded by washing in with propylene (200 mL). After the indicated time,typically one hour, the reactor was vented to about 170 psig pressureand then an ethylene/propylene gas mixture was passed through thereactor at the rates indicated while maintaining 200 psig. At the end ofthe gas phase stage, typically 90 to 150 minutes, the reactor was ventedand cooled under N2. The granular ICP polymer was removed and dried.

Polymerization run numbers 1-14 were made using Supported ComparisonMetallocene Catalyst System 1. Results are reported in Tables 1 and 2.

Polymerization run numbers 15-25 made using Supported ComparisonMetallocene Catalyst System 2 Results are reported in Tables 3 and 4.

Polymerization run numbers 26-39 were made using Supported MetalloceneCatalyst System 3A. Results are reported in Tables 5 and 6.

Polymerization run numbers 4045 were made using Supported MetalloceneCatalyst System 3B. Results are reported in Tables 7 and 8.

Polymerization run numbers 46 to 4 were made using Supported MetalloceneCatalyst System 3C. Results are reported in Tables 9 and 10.

Polymerization run numbers 65-71 were made using Supported MetalloceneCatalyst System 4. Results are reported in Tables 11 and 12.

Polymerization run numbers 72-88 were made using Supported MetalloceneCatalyst System 5. Results are reported in Tables 13 and 14.

Polymerization run numbers 89-98 were made using Supported MetalloceneCatalyst System 6. Results are reported in Tables 15 and 16.

Polymerization run numbers 99-111 were made using Supported MetalloceneCatalyst System 7. Results are reported in Tables 17 and 18.

Polymerization run numbers 112-116 were made using Supported MetalloceneCatalyst System 8. Results are reported in Tables 19 and 20.

Polymerization run numbers 117-132 were made using Supported MetalloceneCatalyst System 9. Results are reported in Tables 21 and 22.

Polymerization run numbers 133 and 134 were made using SupportedMetallocene Catalyst System 10. Results are reported in Tables 23 and24.

Polymer Analysis

Molecular weight determinations were made by gel permeationchromatography (GPC) according to the following technique. Molecularweights and molecular weight distributions were measured using a Waters150C gel permeation chromatography equipped with Shodex (Showa Denko)AT-806MS columns and a differential refractive index (DRI) detectoroperating at 145° C. with 1,2,4-trichlorobenzene as the mobile phase ata 1.0 mL/min. flow rate. The sample injection volume was 300microliters. The columns were calibrated using narrow polystyrenestandards to generate a universal calibration curve. The polypropylenecalibration curve was established using k=8.33×10⁻⁵ and a=0.800 as theMark-Houwink coefficients. The numerical analyses were performed usingWaters “Expert-Ease” software running on a VAX 6410 computer.

Ethylene amounts in the random copolymers were determined by FT-IR usinga calibration obtained from samples whose composition was determined byNMR

DSC melting points were determined on commercial DSC instruments and arereported as the second melting point. The polymer granules weighing lessthan 10 milligrams were heated to 230.0° C. for ten minutes and thencooled from 230° C. to 50° C. at 10° C./minute. The sample is held at50° C. for five minutes. The second melt is then recorded as the sampleis heated from 50° C. to 200° C. at a rate of 10° C./minute. The peaktemperature is recorded as the second melting point.

ICP Polymer Extraction Method

The ICP polymer was dissolved in hot xylene and then allowed to coolovernight. After filtration the insolubes are dried. The xylene solubleportion was evaporated and the soluble material recovered. The IV of therecovered soluble material was measured in decalin at 135° C. by usingknow methods and instruments such as a Schott A VSPro ViscosityAutomatic Sampler.

At very high ICP MFR this method can extract some low molecular weightisotactic PP and thus lower the observed IV.

ICP Polymer Fractionation Method

The ICP samples were sent to Polyhedron Laboratories, Inc. to befractionated and analyzed by GPC. A generally described of the procedureis found in the reference J. C. Randall, J. Poly. Sci.: Part A PolymerChemistry, Vol. 36, 1527-1542 (1998).

TABLE 1 racemic dimethylsiladiyl(2-methyl-4-phenylindenyl)₂ zirconiumdichloride/MAO - comparison Metallocene Catalyst Cat Time C₂ ⁼/C₃ ⁼System TEMP. Amount Yield Efficiency C2 = H2 split flow rates RUN #(Comparison) (° C.) (mg) (g) (Kg/g cat) (delta psi) (delta psi) (min.)(l/min.) 1 1 60 67 274.7 4.10 0 0 60 — 2 1 60 45 71.7 1.59 0 0 60 — 3 160 40 134.1 3.35 10 0 60 — 4 1 60 42 221.5 5.27 20 0 60 — 5 1 60 30121.3 4.04 55 0 60 — 6 1 60 30 130.2 4.34 70 0 60 — 7 1 60 30 101.8 3.3920 0 60 — 8 1 70 45 293.5 6.52 — 50 60 — 9 1 70 31 198.9 6.42 — 50 60 —10 1 70 30 291.9 9.73 — 50  60/150 4.0/1.0 11 1 70 30 231.3 7.71 — 5060/90 4.0/1.0 12 1 70 30 224.8 7.49 — 50 60/90 4.1/0.9 13 1 70 30 209.97.00 — 50 60/90 3.6/1.4 14 1 70 30 208.2 6.94 — 50 60/90 4.0/1.0

TABLE 2 racemic dimethylsiladiyl(2-methyl-4-phenylindenyl)₂ zirconiumdichloride/MAO - comparison Metallocene Catalyst Total IV System TotalEthylene Ethylene in Rubber Final MFR Melting Point Of RUN #(Comparison) (wt %) Rubber (wt %) (wt %) (g/10 min.) (° C.) MW MWDCopolymer 1 1 — — — 0.16 149.2 600.0 2.00 — 2 1 — — — 0.54 148.2 664.91.92 — 3 1 0.67 — — 0.84 142.0 349.0 2.09 — 4 1 1.28 — — 2.57 138.4230.0 1.95 — 5 1 3.77 — — 6.48 121.4 255.0 2.04 — 6 1 4.43 — — 5.95116.0 301.0 2.30 — 7 1 1.44 — — 2.05 137.5 330.4 2.23 — 8 1 — — — 99.6150.3 120.6 3.01 — 9 1 — — — 58.95 150.9 135.7 3.15 — 10 1 13.23  49.2026.89 178.5 151.2 81.2 3.37  0.7520 11 1 7.58 47.37 16.00 134.05 150.698.4 3.25 0.687 12 1 7.82 50.04 15.63 127.16 150.0 100.4 3.11 0.708 13 15.3  38.96 13.60 201.9 150.43 91.2 3.28 0.779 14 1 0.47 64.32  0.73 97.1150.8 116.8 3.42 not submit.

TABLE 3 racemicdimethylsiladiyl(2-methyl-4-[1-naphthy]indenyl)₂zirconiumdichloride/MAO - comparison Metallocene Cat Time Catalyst Amount YieldEfficiency C2 = H2 split C₂ ⁼/C₃ ⁼ flow RUN # System (mg) (g) (kg/g cat)(delta psi) (delta psi) (min.) rates (l/min.) 15 2 76 332.0 4.37 — 40 60— 16 2 61 260.8 4.28 — 35 60/120 4.0/1.0 17 2 60 266.2 4.44 — 35 60/1204.4/0.6 18 2 60 272.6 4.54 — 35 60/120 4.2/0.8 19 2 61 196.9 3.23 — 3560 — 20 2 61 121.2 1.99 20 5 60 — 21 2 61 118.1 1.94 30 5 60 — 22 2 61137.7 2.26 40 5 60 — 23 2 62 141.9 2.29 50 5 60 — 24 2 60 138.6 2.31 4010 60 — 25 2 62 234.8 3.79 — 50 60/90  4.0/1.0

TABLE 4 racemicdimethylsiladiyl(2-methyl-4-[1-naphthyl]indenyl)₂zirconiumdichloride/MAO - comparison Metallocene Total Final Catalyst TotalEthylene Ethylene in Rubber MFR Melting Point RUN # System (wt %) Rubber(wt %) (wt %) (g/10 min.) (° C.) MW MWD IV of Copolymer 15 2 — — — 4.08150.5 299.1 2.78 — 16 2 7.76 47.27 16.42 4.76 151.7 212.1 2.68 1.6567 172 16.39 61.45 26.67 1.3 150.8 230.9 3.33 1.7048 18 2 9.74 51.52 18.914.98 151.0 210.4 2.96 1.7127 19 2 — — — 3.12 151.0 278.0 2.49 — 20 21.27 — — 0.19 138.43 603.0 2.59 — 21 2 1.75 — — 0.15 136.10 614.8 2.59 —22 2 2.25 — — 0.196 131.90 604.5 2.31 — 23 2 2.82 — — 0.213 127.83 579.02.36 — 24 2 2.39 — — 0.225 131.63 542.8 2.41 — 25 2 3.803 48.39  7.864.95 151.43 176.8 2.94 1.425 

TABLE 5 racemicdimethylsiladiyl-bis-(4-(3′,5′-di-terbutylphenyl)-2-methylindenyl)zirconium dichloride/MAO Metallocene Cat Time C₂ ⁼/C₃ ⁼ Catalyst AmountTemp. Yield Efficiency C2 = H2 split flow rates RUN # System (mg) (° C.)(g) (Kg/g cat) (delta psi) (delta psi) (min.) (l/min.) 26 3A 46 60 37.80.82 — 0 60 — 27 3A 47 60 83.4 1.8  5 0 60 — 28 3A 45 60 125.8 2.8 10 060 — 29 3A 46 60 135.0 2.9 20 0 60 — 30 3A 45 60 268.7 6.0 35 0 58 — 313A 20 70 111.2 5.6 — 35 60 — 32 3A 32 70 192.8 6.0 — 35 60 — 33 3A 32 70186.9 5.8 — 25 60/60 4.0/1.0 34 3A 33 70 227.0 6.9 — 35 60/90 4.0/1.0 353A 33 70 245.5 7.4 — 35  60/120 4.0/1.0 36 3A 32 70 204.9 6.4 — 35 60/903.6/1.4 37 3A 30 70 194.7 6.5 — 35  45/120 4.0/1.0 38 3A 30 70 238.0 7.9— 35  60/120 4.4/0.6 39 3A 33 70 266.9 8.1 — 35  60/120 4.2/0.8

TABLE 6 racemicdimethylsiladiyl-bis-(4-(3′,5′-di-tertbutylphenyl)-2-methylindenyl)zirconium dichloride/MAO Metallocene Total Ethylene in Total CatalystEthylene Rubber Rubber Final MFR Melting Point IV of RUN # System (wt %)(wt %) (wt %) (g/10 min.) (° C.) MW MWD Copolymer 26 3A — — — 0.12156.63 681.3 2.44 — 27 3A 0.095 — — 0.6 153.77 569.1 2.43 — 28 3A 0.34 —— 1.63 150.23 428.2 2.49 — 29 3A 1.3 — — 2.65 144.43 316.8 1.91 — 30 3A1.8 — — 4.78 140.97 271.4 1.86 — 31 3A — — — 15.03 156.77 192.9 2.37 —32 3A — — — 6.88 157.37, 220.4 2.50 — 143.3 minor 33 3A 4.58 41.88 10.97.37 156.57 267.8 3.65 1.003 34 3A 3.87 41.02 9.43 15.37 156.97 185.23.21 0.957 35 3A 6.18 41.17 15.0 15.88 157.17 172.2 3.44 0.841 36 3A3.84 27.28 14.1 12.76 156.50 227.4 3.32 0.824 37 3A 7.45 39.17 19.018.61 156.83 163.8 3.23 0.844 38 3A 11.19 54.72 20.4 6.76 157.37 233.53.62 1.039 39 3A 7.88 46.66 16.9 12.75 156.43 194.6 3.17 0.876

TABLE 7 racemicdimethylsiladiyl-bis-(4-(3′,5′-di-tertbutylphenyl)-2-methylindenyl)zirconium dimethyl/NCA Metallocene Cat Time RUN Catalyst Amount Temp.Yield Efficiency H2 split C₂ ⁼/C₃ ⁼ flow NUMBER System (mg) (° C.) (g)(Kg/g cat) (delta psi) (min.) rates (l/min.) 40 3B 47 60 2.9 0.06 0 60 —41 3B 202 60 17.2 0.85 0 60 — 42 3B 33 70 162.9 4.94 35 60 — 43 3B 34 70203.1 5.97 35 60/120 4.2/0.8 44 3B 31 70 187.5 6.05 35 60/120 4.4/0.6 453B 31 70 169.7 5.47 35 60/60  4.2/0.8

TABLE 8 racemicdimethylsiladiyl-bis-(4-(3′,5′-di-tertbutylphenyl)-2-methylindenyl)zirconium dimethyl/NCA Metallocene Total Ethylene in Total IV RUNCatalyst Ethylene Rubber Rubber Final MFR Melting Point of NUMBER System(wt %) (wt %) (wt %) (g/10 min.) (° C.) MW MWD Copolymer 40 3B — — — DNA156.63 821.6 1.98 — 41 3B — — — 0.075 158.43 898.8 — 42 3B — — — 14.7159.1 202.3 2.30 — 43 3B ‘7.284 49.49 14.7 28.01 158.23 161.2 2.40 0.90844 3B 11.13 55.59 20.0 12.3 157.83 180.8 2.29 1.073 45 3B 3.96 48.668.14 23.7 158.1 158.8 2.25 1.055

TABLE 9 racemicdimethylsiladiyl-bis-(4-(3′,5′-di-tertbutylphenyl)-2-methylindenyl)zirconium dimethyl/NCA Metallocene Cat Catalyst Amount Temp. YieldEfficiency C2 = H2 Time RUN # System (mg) (° C.) (g) (Kg/g cat) (deltapsi) (delta psi) (min.) 46 3C 50 70 166.5 3.3 — 50 60 47 3C 50 70 60.91.2 — 25 60 48 3C 50 70 153.4 3.1 — 60 60 49 3C 34 60 17.8 0.52 20 0 6050 3C 35 60 89.1 2.5 20 20 60 51 3C 36 60 96.4 2.7 30 20 60 52 3C 36 6084.9 2.4 50 20 60 53 3C 60 60 130.3 2.2 30 35 40 54 3C 51 70 138.6 2.7 —60 60 55 3C 50 70 65.6 1.3 — 40 60 56 3C 50 70 117.6 2.4 — 55 60 57 3C50 70 65.9 1.3 — 40 60 58 3C 150 70 252.4 1.68 — 40 55 59 3C 101 70191.0 1.9 — 50 60 60 3C 50 70 133.0 2.7 — 55 60 61 3C 51 70 90.7 1.8 —55 60 62 3C 62 60 92.7 1.5 30 10 60 63 3C 51 70 122.3 2.4 — 55 60 64 3C102 70 229.6 2.3 — 55 60

TABLE 10 racemic dimethylsiladiyl-bis-(4-(3′,5′-di-tertbutylphenyl)-2-methylindenyl) zirconium dimethyl/NCA MetalloceneTotal Final Melting RUN Catalyst Ethylene MFR Point # System (wt %)(g/10 min.) (° C.) MW MWD 46 3C — 12.53 157.03 187.7 2.33 47 3C — 0.803156.9 445.3 2.10 48 3C — 109.65 157.5 109.1 2.46 49 3C 1.3 6.92 145.43357.9 1.83 50 3C 1.4 17.01 145.1 203.7 2.04 51 3C 2.1 19.33 139.30 188.71.97 52 3C 3.0 27.96 133.63 162.9 1.76 53 3C 1.7 50.22 142.7 152.3 2.5254 3C — 486 158.23 79.9 2.84 55 3C — 6.2 158.17 338.2 2.77 56 3C — 66.37157.77 133.7 2.60 57 3C — 2.42 158.03 381.7 2.62 58 3C — 5.38 158.3344.6 2.60 59 3C — 15.59 157.97 289.3 2.75 60 3C — 76.4 158.23 125.02.14 61 3C — 5.95 158.63 245.1 2.58 62 3C 1.0 5.93 140.57 277.0 1.83 633C — 6.75 157.7 234.4 3.00 64 3C — 6.3 157.43 240.2 2.52

TABLE 11racemic[9-silafluorenebis(4-(3′,5′-di-t-butylphenyl)-2-methylindenyl]zirconiumdichloride/MAO Metallocene Cat Time Catalyst Amount TEMP. YieldEfficiency H2 split C₂ ⁼/C₃ ⁼ flow RUN # System (mg) (° C.) (g) (Kg/gcat) (delta psi) (min.) rates (l/min.) 65 4 299 60 13.2 0.04 0  6 — 66 461 60 35.0 0.57 0 60 — 67 4 60 70 81.3 1.4 35 60 — 68 4 32 70 96.2 3.035 60/90 4.0/1.0 69 4 30 70 93.3 3.1 35  60/120 4.0/1.0 70 4 31 70 83.92.7 35 60/90 3.6/1.4 71 4 30 70 77.8 2.6 35  60/120 4.2/0.8

TABLE 12racemic[9-silafluorenebis(4-(3′,5′-di-tertbutylphenyl)-2-methylindenyl]zirconiumdichloride/MAO Metallocene Total Ethylene in Total IV Catalyst EthyleneRubber Rubber Final MFR Melting Point of RUN # System (wt %) (wt %) (wt%) (g/10 min.) (° C.) MW MWD Copolymer 65 4 — — — 0.65 156.17 412 149.3— 66 4 — — — 0.075 156.23 710.8 2.71 — 67 4 — — — 3.59 156.5 270.7 2.82— 68 4 4.814 54.74 8.8 69.59 155.43 119.4 3.22 69 4 6.624 49.55 13.49.84 156.5 200.0 3.56 70 4 3.095 42.72 7.2 14.54 155.97 194.5 3.52 71 47.691 54.36 14.1 10.61 157.17 207.1 3.50

TABLE 13racemic[9-silafluorenebis(4-(3′,5′-di-t-butylphenyl)-2-isopropylindenyl]zirconiumdichloride/MAO Metallocene Cat Time Catalyst Amount TEMP. YieldEfficiency C2= H2 split C₂ ⁼/C₃ ⁻flow RUN # System (mg) (° C.) (g) (Kg/gcat) (delta psi) (delta psi) (min.) rates (l/min.) 72 5 300 60 11.8 0.04— 0 10 — 73 5 120 70 116.8 0.97 — 10 60 — 74 5 121 70 127.6 1.1 — 1060/90 4.0/1.0 75 5 62 70 126.4 2.0 — 20 60 — 76 5 63 70 139.5 2.2 — 3560 — 77 5 60 70 151.4 0.40 — 20 60/90 4.2/0.8 78 5 62 70 246.2 4.0 — 3560/90 4.2/0.8 79 5 60 70 218.9 3.6 — 35  60/120 4.2/0.8 80 5 62 70 249.84.0 — 50 60 — 81 5 61 70 233.1 3.8 — 35  60/120 4.4/0.6 82 5 61 60 184.23.0 10 20 60 — 83 5 60 60 202.6 3.4 20 20 60 — 84 5 60 60 209.6 3.5 3020 60 — 85 5 60 70 157.9 2.6 — 35  30/120 4.4/0.6 86 5 63 70 200.5 3.2 —35 60 — 87 5 60 70 223.9 3.7 — 35  60/120 4.2/0.8 88 5 60 70 196.1 3.3 —35  60/180 4.2/0.8

TABLE 14racemic[9-silafluorenebis(4-(3′,5′-di-t-butylphenyl)-2-isopropylindenyl]zirconiumdichloride/MAO Metallocene Total Ethylene in Total IV Catalyst EthyleneRubber Rubber Final MFR Melting Point of RUN # System (wt %) (wt %) (wt%) (g/10 min.) (° C.) MW MWD Copolymer 72 5 — — — 0.82 160.78 381.6 2.01— 73 5 — — — 2.85 159.17 267.3 1.80 — 74 5 4.297 32.93 13.0  3.56 161.1255.7 2.03 2.92 75 5 — — — 11.53 158.83 191.5 2.25 — 76 5 — — — 24.03159.43 166.6 1.98 — 77 5 2.449 32.63 7.5 12.0 159.7 194.7 2.11 2.06 78 52.012 42.53 4.7 110.44 159.1 116.8 2.48 2.21 79 5 3.389 40.38 8.4 32.37158.5 173.2 2.71 2.55 80 5 — — — 499.99 157.9 85.7 2.25 — 81 5 4.09347.35 8.6 41.24 158.57 147.0 2.32 2.87 82 5 0.87 — — 9.54 151.17 204.22.39 — 83 5 1.4 — — 18.53 146.17 182.3 2.14 — 84 5 2.4 — — 24.5 138.5172.2 1.93 — 85 5 4.732 46.4  10.2  118.7 158.23 119.7 2.39 86 5 — — —28.17 158.37 — 87 5 3.081 44.21 7.0 61.24 158.83 88 5 — — — 15.7 158.77—

TABLE 15dimethylsiladiyl-bis-(2-methyl-4-(3′,5′-di-methylphenyl)indenyl)zirconiumdichloride/MAO Metallocene Cat Time C₂ ⁼/C₃ ⁼ RUN Catalyst TEMP. AmountYield Efficiency C2 = H2 split flow rates # System (° C.) (mg) (g) (Kg/gcat) (delta psi) (delta psi) (min.) (l/min.) 89 6 60 45 72.7 1.6  0 0 60— 90 6 60 45 111.9 2.5  5 0 60 — 91 6 60 47 155.6 3.3 10 0 60 — 92 6 6046 204.9 4.5 20 0 60 — 93 6 60 45 244.5 5.4 35 0 60 — 94 6 70 30 251.28.4 — 35 60/90 4.0/1.0 95 6 70 30 236.8 7.9 — 35 60/90 3.6/1.4 96 6 7032 259.5 8.7 — 35 60/90 4.2/0.8 97 6 70 33 249.4 7.6 — 35 60/90 4.4/0.698 6 70 33 186.8 5.7 — 35 60

TABLE 16dimethylsiladiyl-bis-(2-methyl-4-(3′,5′-di-methylphenyl)indenyl)zirconiumdichloride/MAO Metallocene Total Ethylene in Total IV Catalyst EthyleneRubber Rubber Final MFR Melting Point of RUN # System (wt %) (wt %) (wt%) (g/10 min.) (° C.) MW MWD Copolymer 89 6 — — — 0.0245 150.9 937.72.10 — 90 6 — — — 0.17 148.3 671.3 2.15 — 91 6 0.18 — — 0.59 145.03463.6 2.01 — 92 6 1.1 — — 2.68 140.9 303.8 1.89 — 93 6 1.8 — — 3.98135.43 255.7 1.74 — 94 6 8.11 49.7 16.3 4.54 152.57 281.1 3.51 0.866 956 5.34 40.32 13.2 6.25 151.97 284.5 3.57 0.861 96 6 9.98 58.47 17.1 7.07152.43 220.4 3.00 1.420 97 6 14.42 61.66 23.4 19.43 152.1 179.4 2.571.091 98 6 — — — 1.79 151.30 327.9 1.98 —

TABLE 17dimethylsiladiyl-bis-(4-(3′,5′-bistrifluoromethylphenyl)-2-methyl-indenyl)zirconium dichloride/MAO TEAL Cat Time C₂ ⁼/C₃ ⁼ Metallocene AmountAmount Yield Efficiency H2 split flow rates RUN # Catalyst System (mls)(mg) (g) (Kg/g cat) (delta psi) (min.) (l/min.) 99 7 0.3 45 5.4 0.12 060 — 100 7 0.3 31 82.0 2.6 35 60 — 101 7 0.3 21 47.3 2.3 35 60 — 102 70.3 30 102.0 3.4 35 60/90 4.0/1.0 103 7 0.3 32 95.2 3.0 35 60/90 3.6/1.4104 7 0.3 30 97.9 3.3 35  60/120 4.0/1.0 105 7 0.3 32 98.1 3.1 35 90/120 4.4/0.6 106 7 0.3 30 97.3 3.2 35  60/120 4.2/0.8 107 7 0.3 3244.7 1.4 35  45/120 4.0/1.0 108 7 0.3 60 88.7 1.5 20 109 7 0.3 61 110.81.8 20 60/90 4.0/1.0 110 7 0.3 61 134.0 2.2 20 60/90 3.6/1.4 111 7 0.361 134.2 2.2 20 60/90 4.2/0.8

TABLE 18dimethylsiladiyl-bis-(4-(3′,5′-bistrifluoromethylphenyl)-2-methyl-indenyl)zirconium dichloride/MAO Metallocene Total Ethylene in Total Melting IVCatalyst Ethylene Rubber rubber Final MFR Point of RUN # System (wt %)(wt %) (wt %) (g/10 min.) (° C.) MW MWD Copolymer 99 7 — — — — 154.5606.8* 3.32 — 100 7 — — —  31.06 155.23 159.9 3.99 — 101 7 — — —  28.75156.5 172.8 3.74 — minor 142.98 102 7 5.829 52.53 11.1 341.43 154.3 87.43.75 1.45 103 7 3.784 44.54 8.5 185.49 154.83 101.8 3.97 0.74 104 79.308 52.05 17.9 102.01, 154.7 110.8 3.17 0.80  93.56 105 7 13.09 61.0921.4 134.68, 154.5 100.0 3.22 1.03 127.37 106 7 15.59 55.49 28.0  36.04,155.23 148.8 3.40 0.89  32.5 107 7 9.271 51.57 18.0 356.35, 154.3 78.93.60 0.77 348.24 108 7 — —  4.08, 155.43 285.0 2.93  5.64 109 7 11.7550.58 23.2  17.27, 154.57 219.5 4.26 0.79  18.28 110 7 11.75 40.45 29.0 35.6 154.70 202.9 4.69 0.78 111 7 14.84 55.87 26.6  14.8 154.70 204.24.24 0.84

TABLE 19dimethylsiladiylbis(4-(3′,5′,-bis-trimethylsilyl-phenyl)-2-methylindenyl)zirconium dichloride/MAO Metallocene Cat Time Catalyst Amount TEMP YieldEfficiency H2 split C₂ ⁼/C₃ ⁼ flow RUN # System (mg) (° C.) (g) (Kg/gcat) (delta psi) (min.) rates (l/min.) 112 8 60 60 40.8 0.68 0 60 — 1138 31 70 107.3 3.5 35 60 — 114 8 30 70 123.6 4.1 35 60/90 4.0/1.0 115 830 70 112.2 3.7 35 60/90 3.6/1.4 116 8 30 70 123.8 4.1 35 60/90 4.4/0.6

TABLE 20dimethylsiladiylbis(4-(3′,5′-bis-trimethylsilyl-phenyl)-2-methylindenyl)zirconium dichloride/MAO Metallocene Total Ethylene in Total Melting IVCatalyst Ethylene Rubber rubber Final MFR Point of RUN # System (wt %)(wt %) (wt %) (g/10 min.) (° C.) MW MWD Copolymer 112 8 — — — 0.13 155.3594.2 1.92 — 113 8 — — — 3.59 155.77 269.8 2.19 — 114 8 4.148 44.34  9.461.05 156.1 128.1 2.79 115 8 4.069 24.09 16.9 19.73 156.97 171.4 3.00116 8 6.852 52.48 13.1 12.82 156.5 155.6 3.71

TABLE 21dimethylsiladiylbis[4-(3′,5′,dimethylphenyl)-2-isopropylindenyl]-zirconium dichloride/MAO Metallocene Cat Time Catalyst Amount TEMP YieldEfficiency H2 split C₂ ⁼/C₃ ⁼ flow RUN # System (mg) (° C.) (g) (Kg/gcat) (delta psi) (min.) rates (l/min.) 117 9 304 60 16.6 0.05 0 60 — 1189 300 70 47.5 0.16 5 20 — 119 9 60 70 25.5 0.43 5 60 — 120 9 121 70 63.00.52 5 60 — 121 9 120 70 79.4 0.66 5 60/90 4.0/1.0 122 9 122 70 99.10.81 5 60/90 4.1/0.9 123 9 123 70 71.2 0.57 5 60/90 3.6/1.4 124 9 120 7095.2 0.79 5  60/120 4.0/1.0 125 9 121 70 143.7 1.2 10 60/90 4.0/1.0 1269 124 70 167.6 1.4 10 60/90 4.2/0.8 127 9 120 70 101.5 0.85 10 60 — 1289 121 70 121.2 1.0 10 60/90 4.4/0.6 129 9 121 70 167.6 1.4 20 60 — 130 9124 70 259.3 2.1 35 60 — 131 9 30 70 99.3 3.31 35 60/90 4.0/1.0 132 9 3370 80.3 2.4 35 60 —

TABLE 22dimethylsiladiylbis[4-(3′,5′-dimethylphenyl)-2-isopropylindenyl]zirconiumdichloride/MAO Metallocene Total Ethylene in Total IV Catalyst NotebookEthylene Rubber rubber Final MFR Melting Point of RUN # System (21810-)(wt %) (wt %) (wt %) (g/10 min.) (° C.) MW MWD Copolymer 117 9 077 — — —25.61 154.5 167.1 39.73 — 118 9 078 — — — 175.39 151.97 129.2 4.86 — 1199 079 — — — 87.33 152.03 134.5 3.39 — 120 9 080 — — — 76.55 151.83 138.52.20 — 121 9 081 8.199 39.92 20.5 14.16 153.43 213.6 3,05 2.833 122 9082 7.068 42.81 16.5 15.43 152.03 196.3 3.01 2.505 123 9 083 8.294 26.5231.3 4.92 152.77 248.0 3.28 2.662 124 9 084 15.85 39.17 40.5 0.479153.23 306.7 4.14 3.667 125 9 086 7.521 37.72 19.9 27.72 153.03 204.73.61 2.202 126 9 087 10.02 44.73 22.4 5.8 152.63 235.8 3.58 3.508 127 9089 — — — 75.86 151.03 135.8 2.30 — 128 9 097 21.21 56.17 37.8 0.53152.10 280.9 3.84 3.356 129 9 104 — — — 84.22 151.83 136.1 2.31 — 130 9105 — — — 511.36 150.17 88.7 2.47 — 131 9 106 2.133 44.04 4.84 824.95150.17 83.6 2.95 1.29  132 9 107 — — — 906.0 150.30 82.9 2.65 —

TABLE 23 [9-silafluorenebis(4-(3′,5′-diemthylphenyl)-2-isopropylindene]-zirconium dichloride/MAO Metallocene Cat Catalyst TEMP. Amount YieldEfficiency H2 Time RUN # System (° C.) (mg) (g) (Kg/g cat) (delta psi)(min.) 133 10 60 302 6.0 0.02 0 60 134 10 70 121 18.4 0.15 10 60

TABLE 24 [9-silafluorenebis(4,(3′,5′-dimethylphenyl)-2-isopropylindene]-zirconium dichloride/MAO Metallocene Catalyst Final MFR Melting PointRUN # System (g/10 min.) (° C.) MW MWD 133 10 — 150.9, 467.6 4.98 minor156.52 134 10 32.07 156.5 104.8 2.71

While the present invention has been described and illustrated byreference to particular embodiments, it will be appreciated by those ofordinary skill in the art, that the invention lends itself to manydifferent variations not illustrated herein. For these reasons, then,reference should be made solely to the appended claims for purposes ofdetermining the true scope of the present invention.

We claim:
 1. A compound represented by the formula:

wherein: M¹ is selected from the group consisting of titanium,zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenumand tungsten; R¹ and R² are identical or different, and are one of ahydrogen atom, a C₁-C₁₀ alkyl group, a C₁-C₁₀ alkoxy group, a C₆-C₁₀aryl group, a C₂-C₄₀ alkenyl group, a C₇-C₄₀ arylalkyl group, a C₇-C₄₀alkylaryl group, a C₉-C₄₀ arylalkenyl group, an OH group or a halogenatom, or a conjugated diene which is optionally substituted with one ormore hydrocarbyl, tri(hydrocarbyl)silyl groups ortri(hydrocarbyl)silylhydrocarbyl groups, said diene having up to 30atoms not counting hydrogen; R³ are identical or different and are eacha hydrogen atom, a halogen atom, a C₁-C₁₀ alkyl group which may behalogenated, a C₆-C₁₀ aryl group which may be halogenated, a C₂-C₁₀alkenyl group, a C₇-C₄₀ arylalkyl group, a C₇-C₄₀ alkylaryl group, aC₈-C₄₀ arylalkenyl group, a —NR′₂, —SR′, —OR′, —OSiR′₃ or —PR′₂ radical,wherein R′ is one of a halogen atom, a C₁-C₁₀ alkyl group, or a C₆-C₁₀aryl group; R⁴ to R⁷ are identical or different and are hydrogen, asdefined for R³ or two or more adjacent radicals R⁵ to R⁷ together withthe atoms connecting them form one or more rings;

 —B(R¹⁴)—, —Al(R¹⁴)—, —Ge—, —Sn—, —O—, —S—, —SO—, —SO₂—, —N(R¹⁴)—, —CO—,—P(R¹⁴), or —P(O)(R¹⁴)—, or an amidoborane radical; wherein: R¹⁴, R¹⁵and R¹⁶ are identical or different and are a hydrogen atom, a halogenatom, a C₁-C₂₀ alkyl group, a C₁-C₂₀ fluoroalkyl or silaalkyl group, aC₆-C₃₀ aryl group, a C₆-C₃₀ fluoroaryl group, a C₁-C₂₀ alkoxy group, aC₂-C₂₀ alkenyl group, a C₇-C₄₀ arylalkyl group, a C₈-C₄₀ arylalkenylgroup, a C₇-C₄₀ alkylaryl group, or R¹⁴ and R¹⁵, together with the atomsbinding them, form a cyclic ring; or R¹³ is represented by the formula:

wherein: R¹⁷ to R²⁴ are one of a hydrogen atom, a C₁-C₁₀ alkyl group, aC₁-C₁₀ alkoxy group, a C₆-C₁₀ aryl group, a C₆-C₁₀ aryloxy group, aC₂-C₄₀ alkenyl group, a C₇-C₄₀ arylalkyl group, a C₇-C₄₀ alkylarylgroup, a C₈-C₄₀ arylalkenyl group, an OH group, or a halogen atom, ortwo or more adjacent radicals R¹⁷ to R²⁴, including R²⁰ and R²¹,together with the atoms connecting them form one or more rings; M² isone or more carbons, silicon, germanium or tin; R⁸, R¹⁰ and R¹² areidentical or different and have the meanings stated for R⁴ to R⁷; and R⁹and R¹¹ are identical or different and are each primary, secondary ortertiary butyl groups.
 2. The compound of claim 1 wherein R³ areidentical C₁-C₄ alkyl groups.
 3. The compound of claim 1 wherein R³ areidentical C₃ alkyl groups.
 4. The compound of claim 1 wherein R⁴ to R⁷are hydrogen atoms.
 5. The compound of claim 1 wherein R⁴ to R⁷ and R¹⁴to R¹⁶ are hydrogen atoms.
 6. The compound of claim 1 wherein R⁹ and R¹¹are both tertiary butyl groups.
 7. The compound of claim 1 wherein R⁴ toR⁷ and R¹⁴ to R¹⁶ are hydrogen atoms and R⁹ and R¹¹ are both tertiarybutyl groups.
 8. A compound represented by the formula:

wherein: M¹ is selected from the group consisting of titanium,zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenumand tungsten; R¹ and R² are identical or different, and are one of ahydrogen atom, a C₁-C₁₀ alkyl group, a C₁-C₁₀ alkoxy group, a C₆-C₁₀aryl group, a C₂-C₄₀ alkenyl group, a C₇-C₄₀ arylalkyl group, a C₇-C₄₀alkylaryl group, a C₈-C₄₀ arylalkenyl group, an OH group, or aconjugated diene which is optionally substituted with one or morehydrocarbyl, tri(hydrocarbyl)silyl groups ortri(hydrocarbyl)silylhydrocarbyl groups, said diene having up to 30atoms not counting hydrogen; R³ are identical and are each a C₁-C₁₀alkyl group; R⁴ to R⁷ are identical or different and are hydrogen, asdefined for R³ or two or more adjacent radicals R⁵ to R⁷ together withthe atoms connecting them form one or more rings;

 —B(R¹⁴)—, —Al(R¹⁴)—, —Ge—, —Sn—, —O—, —S—, —SO—, —SO₂—, —N(R¹⁴)—, —CO—,—P(R¹⁴)—, or —P(O)(R¹⁴)—, or an amidoborane radical; wherein: R¹⁴, R¹⁵and R¹⁶ are identical or different and are a hydrogen atom, a halogenatom, a C₁-C₂₀ alkyl group, a C₁-C₂₀ fluoroalkyl or silaalkyl group, aC₆-C₃₀ aryl group, a C₆-C₃₀ fluoroaryl group, a C₁-C₂₀ alkoxy group, aC₂-C₂₀ alkenyl group, a C₇-C₄₀ arylalkyl group, a C₉-C₄₀ arylalkenylgroup, a C₇-C₄₀ alkylaryl group, or R¹⁴ and R¹⁵, together with the atomsbinding them, form a cyclic ring; or R¹³ is represented by the formula:

wherein: R¹⁷ to R²⁴ are one of a hydrogen atom, a C₁-C₁₀ alkyl group, aC₁-C₁₀ alkoxy group, a C₆-C₁₀ aryl group, a C₂-C₄₀ alkenyl group, aC₇-C₄₀ arylalkyl group, a C₇-C₄₀ alkylaryl group, a C₈-C₄₀ arylalkenylgroup, an OH group or a halogen atom, or two or more adjacent radicalsR¹⁷ to R²⁴, including R²⁰ and R²¹, together with the atoms connectingthem form one or more rings; M² is one or more carbons, silicon,germanium or tin; R⁸, R¹⁰ and R¹² are identical or different and havethe meanings stated for R⁴ to R⁷; and R⁹ and R¹¹ are identical ordifferent and are each primary, secondary or tertiary butyl groups. 9.The compound of claim 8 wherein R⁴ to R⁷ are hydrogen atoms.
 10. Thecompound of claim 8 wherein R⁴ to R⁷ and R¹⁴ to R¹⁶ are hydrogen atoms.11. The compound of claim 8 wherein R³ are both C₃ alkyl groups and R⁹and R¹¹ are both tertiary butyl groups.
 12. The compound of claim 8wherein R⁴ to R⁷ and R¹⁴ to R¹⁶ are hydrogen atoms and R⁹ and R¹¹ areboth tertiary butyl groups.